The reaction of Salen‐like ZnII and NiII precursors with carbacylamidophosphate lanthanide moieties yields six new types of 3d–4f compounds. The complexes were characterized by means of 1H, 31P NMR and IR spectroscopy, elemental analysis, ESI mass spectrometry, and X‐ray diffraction analysis. Depending on the Schiff base ligands, the NiII ion adopts either a square‐planar or an octahedral geometry, whereas the ZnII ion has a tetragonal‐pyramidal geometry. The coordination number of lanthanides is nine or ten. Hydrolytic activities of some heterobimetallic Zn–Ln and Ni–Ln coordination compounds in the reaction of intramolecular hydrolytic degradation of the 2‐(hydroxypropyl)‐p‐nitrophenyl phosphate were investigated. Synthesis and crystal studies of new binuclear 3d–4f complexes based on lanthanide motifs with carbacylamidophosphate ligands and moieties of ZnII and NiII with Schiff bases were carried out. The ability of the system to catalyze the intramolecular transesterification of 2‐(hydroxypropyl)‐p‐nitrophenyl phosphate, which is extensively employed as an RNA model substrate, was tested.