Paltrow, 41, who previously appeared on the show for three episodes, will reprise her role as a substitute teacher Holly Holiday. She won an Emmy Award in 2011 for her guest-starring role on the musical series, reported Ace Showbiz.
Matthew Morrison, 35, who plays Will Schuester, said Crawford would portray Biff, "kind of a Yalie degenerate."
"I think he's going to be Dianna Agron's (Quinn) new love interest," he added.
Paltrow is the latest star who will return to 'Glee' for the 100th episode.
The 100th episode will see Sue Sylvester finally succeeding in her attempt to end the Glee club in Lima. It will also feature the cast singing songs which they've performed in past seasons.
The episode would be airing in two parts on March 18 and 25.
