During the opening moves of a chess game, a player (typically White) may offer a number of gambits, which involve sacrificing a chess piece for an opponent for capture to achieve long‐term positional advantages. One of the most popular gambits is called the Queen's Gambit and involves White offering a pawn to Black, which will open a lane for White's Queen if accepted by Black. In the present study, the generalized matching law (GML) was applied to chess openings involving the Queen's Gambit using over 71,000 archived chess games. Overall, chess players' opening moves involving the Queen's Gambit exhibited orderly matching as predicted by the GML, and the GML accounted for more variance in players' chess decision making as their relative playing experience increased. This study provides support for the generality of the GML and its application to complex operant behavior outside of laboratory contexts.