Palladium-catalyzed amino- and alkoxycarbonylation reactions of aryl iodides were investigated in the presence of aliphatic heterobifunctional N,O-nucleophiles. Selective synthesis of amide alcohols and amide esters was realized, controlled by the base and substrate ratio. The effect of iodobenzene substituents was also studied with surprising results in terms of product selectivity. In addition to the model ethanolamine/iodobenzene system, various heteroaromatic substrates and numerous related nucleophiles were tested under optimized conditions, providing moderate to good yields of the target compounds. Reactions of serinol and 1,3-diamino-2-propanol as model trifunctional compounds showed particularly high chemoselectivity on amide ester products. Considering the coordinative properties of the applied nucleophiles, a rational catalytic cycle was proposed.