A highly selective synthesis of acyl isoureas and imides from readily accessible amides, isocyanides, alcohols and carboxylates based on reaction solvent selection is described. In the presence of a catalytic amount of [1,1′‐bis(diphenylphosphino)ferrocene]dichloropalladium(II) and cupric acetate, treatment of amides and isocyanides in alcohols at 60 °C provided acyl isoureas in high yields. Interestingly, when other solvents such as acetonitrile was used instead of alcohols, imides were exclusively produced in good to excellent yields via direct N‐acylation of amides with carboxylates as the acyl sources. This protocol offers an attractive alternative approach toward isoureas and imides.magnified image