Here are a few women-centric pieces that I've enjoyed over the past few years, grouped by fandom:
Angel -
An Alphabet of Fred by
deird1, PG-13 (Gen) - Excellent character study of both Fred and Illyria
Buffy the Vampire Slayer -
A Promise by
silver_galaxy, G (Gen) - A nice look at the depth of the bond between Buffy and Dawn
Firefly -
Enough for Now by
rivendellrose, NC-17 (Femslash) - The evolution of the relationship of River and Zoe, takes place post Serenity (aka the BDM)
Life -
All Fall Down by
rose_griffes, PG-13 (Gen) - Brilliant piece about what happened to Rachel Seybolt after she left town.
Mad Men -
Old Wounds by
falafel_musings, PG-13 (Het/Gen)- A look at Peggy and Pete's relationship after the confession at the end of season 2 - the first section is from Peggy's point-of-view
OZ -
Guardian by
trillingstar, not-rated, but somewhere in the PG-13/R range (Gen) - This is a very strong portrayal of the relationship of a grandmother and granddaughter who have been marked by tragedy. Neither Holly nor Victoria Beecher were major characters on the show, but this fic does an incredible job of filling in the blanks of who they have become as a result of Tobias Beecher (Holly's father & Victoria's son) being in prison.