Rangers exercised the ghosts of last year's competition by knocking out holders Queen of the South with a 3-0 victory on Wednesday, gaining revenge for their quarter-final defeat 12 months ago.
A date has yet to be conformed for the Gers' meeting with the Warriors, while Annan's visit to Fife will take place on Sunday, October 13, with the final to come next April.
Rangers have not faced Stenny since Stephane Guivarc'h and Rod Wallace gave them a 2-0 Scottish Cup win back in 1999, although they struck 10 goals in two away games against East Stirling - the Warriors' Ochilview tenants - last season.
Ally McCoist's side have yet to face their League One rivals this season, with their first meeting to come at Ibrox a week on Saturday.
Raith and Annan, meanwhile, will face each other for the first time in a competitive fixture since the bottom-tier outfit were promoted to the senior ranks in 2008.