Hmm, yeah. Anya did meet Spider-Man twice when she was still Arana, and the Grim Hunt storyline was where she became Spider-Girl with Julia Carpenter's Arachne costume (since Julia had become the new Madame Web when Cassandra Webb passed on her powers before she died). She also participated in Spider-Island, where she (re)gained spider-powers after having somehow lost them, and later Spider-Verse, after which she became one of the Multiverse-traveling Web Warriors --- and was somewhat underused in that series. Last appearance was in Spider-Geddon, mainly the Spider-Girls tie-in mini.