Fancast reports that the actress will feature in the seventh episode, 'Chuck Vs. The First Fight'.
She will play Dasha, "a ruthless operative for the nefarious Volkoff organisation" who is an expert at torturing enemy spies "with small-ish implements".
Gasteyer is known for being a regular cast member on Saturday Night Live from 1996 to 2002. Her most recent television appearance was as Judge Patrice Lessner in an episode of CBS legal drama The Good Wife.
Chuck returns to NBC on September 20. Gasteyer's episode will air on November 1.