A series of rare earth 3-(4′-methylbenzoyl)propanoate (mbp–) complexes [RE(mbp)3(H2O)] (RE = rare earth = Y, La, Ce, Nd, Ho, Er) have been prepared by either metathesis reactions between the corresponding rare earth chloride and Na(mbp) or protolysis of rare earth acetates by the free acid. Single-crystal X-ray diffraction studies of [RE(mbp)3(H2O)] (RE = Ce, Nd) and [Ce(mbp)3(dmso)] reveal a 1D carboxylate-bridged polymeric structure in the solid state, featuring 9-coordinate rare earth ions. X-ray powder diffraction patterns of the bulk materials indicates that all of the [RE(mbp)3(H2O)] complexes except RE = La are isomorphous. Hence, there is no structural change from the complex with RE = Ce to that with RE = Er despite the lanthanoid contraction. The 1H NMR spectra of the RE = Ho or Er complexes in (CD3)2SO show large paramagnetic shifts and broadening of the CH2 resonances, indicating the retention of substantial carboxylate coordination in solution.