New dinuclear rhodium(II) pyrazolate (Pz) complexes of formula Rh₂(3-R,5-R′Pz)₄·2L (R = R′ = CF₃, L = H₂O (1), CH₃CN (2)) and Rh₂(3-R,5-R′Pz)₄ (R = R′ = ^tBu (3); R = CF₃, R′ = ^tBu (4)) have been synthesized from the interaction of the lithium salt of the corresponding pyrazole with Rh₂(OAc)₄ in diethyl ether. The complexes were characterized by X-ray crystallography and spectroscopic methods. They were further evaluated as precursors for the chemical vapor deposition (CVD) of Rh thin films using H₂ as the carrier gas. The resulting films were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS).