A facile, efficient, and general deformylation reaction with a wide‐ranging functional group compatibility has been developed with palladium acetate as a precatalyst under exogenous ligand‐free conditions. The mechanistic details of the palladium‐catalyzed deformylation reaction have been outlined on the basis of a combination of experimental and computational studies. The heterogeneous pathway is predominant for the deformylation, and homogeneous catalysis occurs to a lesser extent. This ligand‐free catalytic cycle is proposed to undergo oxidative addition, migratory extrusion, and reductive elimination as the key steps. Kinetic studies reveal a first‐order rate dependency with respect to the aldehyde. Furthermore, kinetic isotope effects, competition experiments, and Hammett studies suggest that the migratory extrusion step is the rate‐determining step. For the homogeneous pathway, the experimental findings are also supported by DFT studies.