Stille-type cross-coupling between alpha-alkoxy(amino)stannanes and acyl chlorides affords alpha-hetero-substituted ketones in moderate to good yields when cocatalyzed by Pd and Cu(I) salts. The reaction is applicable to a wide range of tin compounds, especially those bearing alpha-electron-withdrawing groups such as benzoyloxy or acetyloxy, although some ethers (e.g., MOM) are also satisfactory. Aromatic acid chlorides give the best yields. Coupling of chiral alpha-alkoxystannanes, readily available by BINAL-H asymmetric reduction of acylstannanes, proceeds with retention of configuration.