We obtained the photoelectron spectra of Rh(CN)- using the negative ion photoelectron velocity-map imaging (NI-PEVMI) technique and revealed the photodesorption process of Rh(CN)-. The vertical detachment energy (VDE) and adiabatic detachment energy (ADE) of Rh(CN)- have both been experimentally reported to be 2.04 (3) eV. The Franck-Condon (FC) simulation of the ground state of Rh(CN)- was conducted to facilitate a more accurate identification of the experimental photoelectron spectra. The existence of isomer Rh(NC)- was confirmed by the FC simulation result. The vibration frequencies of Rh(CN) and Rh(NC) measured by photoelectron spectroscopy are 462 (50) cm-1 and 471 (50) cm-1, respectively. Based on density functional theory, the stable geometries of Rh(CN)n-1/0 (n = 1-3) clusters were obtained, the values of VDEs and ADEs were calculated, and the photoelectron spectroscopy (PES) was simulated. These can provide theoretical guidance for the experimental study of rhodium cyanide complexes in the future. Finally, we also conduct molecular orbital analysis, natural population analysis, natural resonance theory, and electron localization function analysis to further reveal the nature of the interaction between transition metal Rh and (CN)n ligand. Through the study of Rh(CN)n-1/0 (n = 1-3) complexes, it is found that the transition metal rhodium (Rh) is more inclined to cyanide arrangement.