Frustrated Lewis pairs (FLPs) represent a new paradigm of main‐group chemistry. The Lewis acidic centers in FLP chemistry are typically B and Al atoms in the studies reported over the past decade, and most of them are tri‐coordinated with strong electron‐withdrawing groups. Herein, we report a Ga/P system containing an unprecedented four‐coordinated Lewis acidic Ga center. This Ga/P species performs classical addition reactions toward heterocumulenes, alkyne, diazomethane, and transition metal complex. Regioselective formation of the products can be rationalized by DFT calculations.