trans‐Bis(dipeptide ester)palladium 1–6 complexes with a deprotonated amide group were obtained by dehydrochlorination of trans‐Cl2Pd(dipeptide ester)2 or by direct reaction of Na2PdCl4 with dipeptide ester in the presence of sodium methoxide. The structure of Pd(NH2CH2CONCH2CH2CO2CH3)2 (3) was determined by X‐ray diffraction. Addition of NaOCH3 to Pd[NH2C(H)(R)NCH2CH2CO2CH3]2 [R = CH(CH3)24, CH2Ph 5] results in the formation of the corresponding complexes 7, 8 with cyclic tetrapeptides which also can be directly synthesized from the dipeptide ester and Na2PdCl4.