Several characters in the Marvel Universe have taken the mantle of Spider-Woman over the years -- often simultaneously and for drastically different reasons. Here's a chronological breakdown of every Spider-Woman in the main Marvel Universe, Earth-616, as well as when she held the title.
Valerie the Librarian
Predating even Jessica Drew, Valerie the Librarian (Hattie Winston) may very well be Marvel's first Spider-Woman character, first appearing in the educational television series The Electric Company. She was a recurring character in the Spider-Man educational block, "Spidey Super Stories," which helped teach children to read. Valerie didn't have superpowers, but she was the first -- and so far only -- Black Spider-Woman.
Jessica Drew
Jessica Drew is the most well-known Spider-Woman. Debuting in Marvel Spotlight #32, Drew was given powers and brainwashed by HYDRA. Initially serving as one of HYDRA's greatest agents, she soon turned the tables on the evil empire after a confrontation with S.H.I.E.L.D. showed her the full extent of HYDRA's wrong-doing.
Now going by Spider-Woman, Jessica Drew went on to fight on the side of justice. She's undergone a lot over the years, from being replaced by Skrulls, helping bring Carol Danvers out of her tailspin depression and even fighting alien invaders while pregnant. Of all the Spider-Woman, however, Drew is most often dragged into the Spider-Verse conflicts, often playing a key role in the interdimensional battles against the Inheritors.
Julia Carpenter
Julia Carpenter first appeared as Spider-Woman during Secret Wars and became one of the most iconic women to don the costume. Turned into a superhero unwittingly by a secret government agency known as The Commission, Carpenter was first used as a government weapon. She was forced to arrest the X-Men and other superheroes, before having a change of heart and going independent, then working alongside the East and West Coast Avengers.
Carpenter is now Madame Web. She's a single mother, separated from her child during Civil War. She's gone blind and developed psychic abilities as the new Madame Web. She's also famous for her costume, which influenced the design of Peter Parker's symbiote suit.
Mattie Franklin
First appearing in Spectacular Spider-Man #262, Mattie Franklin was a young girl given powers during The Gathering of Five ritual, organized by Norman Osborn. She gained super-strength, agility, light telepathy and telekinesis, then immediately sought out to follow the example of her hero: Peter Parker. Mattie briefly impersonated Spider-Man during a period of time where the wall-crawler had been semi-retired. She later took up the mantle of Spider-Woman.
Mattie temporarily absorbed the powers of the other Spider-Women during a confrontation with Charlotte Witter, proving to be the key to stopping her. Mattie was helped in her studies, ironically, by J. Jonah Jameson, whose then-wife happened to be Mattie's aunt. However, while Mattie's future as a hero looked bright, she was brutally sacrificed in a ritual to raise Kraven the Hunter.
Charlotte Witter
Not all Spider-Woman are created equally. Some, like Charlotte Witter, are actually pretty evil. Witter was the granddaughter of the original Madame Web and a fashion designer who sought power above all else. Her pursuits led her to Doctor Octopus, who helped mutate her into a human/spider hybrid monster. She also gained the ability to absorb spider powers from others.
Setting out on a campaign for power, she temporarily absorbed the powers of other Spider-Women in a bid to defeat Spider-Man, before being stopped by Mattie Franklin, who reabsorbed and redistributed the Spider-Powers Witter robbed. This left Witter in a comatose state, withering away alone.
Veranke
Not all Spider-Woman are humans. Veranke, Queen of the Skrulls, replaced Jessica Drew during Secret Invasion. Her actions led to the coordination of Skrulls all across the world to replace superheroes, preparing for one final strike on Earth to dominate the planet. Several heroes were either put in jeopardy or nearly killed thanks to Veranke's actions, including The Wasp and Kate Bishop.
However, while the heroes did ultimately struggle against the Skrull invasion, Veranke was bested by Wolverine and Hawkeye before being, killed by Norman Osborn, who used his victory against Veranke to become the leader of S.H.I.E.L.D.
Ultimate Jessica Drew
Ultimate Jessica Drew is a fundamentally different character from her Earth-616 counterpart -- even on a genetic level. Ultimate Jessica Drew isn't a victim of HYDRA experimentation, but rather a female clone of Peter Parker.
Despite this origin, Drew went on to be her own hero, adopting the identity of Jessica Drew. This Drew is a lesbian, still pining over all the girls Peter does. She outlives Peter Parker following his tragic battle against the Green Goblin and becomes a mentor figure for Miles Morales once he becomes the new Spider-Man. It's thanks to Jessica that Miles chooses to keep being Spider-Man following a period of incredible self-doubt and existential conflict over being the web-head. Jessica is one of the few Ultimate characters to survive even the destruction of her reality, appearing in Spider-Geddon storyline after the collapse of the Ultimate Universe.