cis-[PdCl₂(CNR)(PPh₃)] [R = Cy, t-Bu, C(Me)₂CH₂C(Me)₃] have been synthesized via the interaction of [(PPh₃)ClPd(μ-Cl)₂PdCl(PPh₃)] with isocyanide in CH₂Cl₂ at room temperature with 90–98% yield and characterized by means of mass spectrometry as well as ¹H, ¹³C{¹H, ³¹P}, and ³¹P{¹H} NMR spectroscopy. The complexes structure in the solid phase has been elucidated by means of X-ray diffraction analysis. Dynamic processes in the solutions of the complexes in CDCl₃ and CD₂Cl₂ at temperature of–95 to 60°С have been studied by means of ¹H and ³¹P NMR spectroscopy. It has been found that the studied compounds existed exclusively in the cis-[PdCl₂(CNR)(PPh₃)] form in the solutions. In the case of cis-[PdCl₂(CNCy)(PPh₃)] in CH₂Cl₂, the conformational transitions of the equilibrium forms (the transition of the substituent in the cyclohexyl cycle between the equatorial and axial positions) are slowed down, the equatorial conformer prevailing in the solution (2: 1 at–95°С). Quantum-chemical simulation (DFT) has revealed that the standard Gibbs energy of the conformational transition from the axial form of cis-[PdCl₂(CNCy)(PPh₃)] into the equatorial one in the CH₂Cl₂ solution at 178 K equals–2.5 kJ/mol, being in agreement with the experimental data.