Ligand-surface interaction of semiconductor nanoparticles (NPs) controls their optoelectronic properties, and thus examination of the interaction is essential for the nanoelectronic applications of NPs. Herein, solid-state nuclear magnetic resonance (NMR) is performed to unravel the ligand-surface interaction in cysteine-capped CdSe magic-sized clusters. N-15-Cd-113 through-bond J-filtered NMR directly shows the presence of the nitrogen-cadmium chemical bond for the first time and indicates that similar to 43% of the amines form the chemical bond. N-15-Cd-113 through-space dipolar-correlated NMR reveals that similar to 54% of the amines locate nearby the surface cadmium with the average nitrogen-cadmium distance of 0.247 nm. The average distance is comparable with that estimated by J-filtered NMR. The difference of the two ratios (similar to 11%) proposes that some amines locate on the surface without forming the chemical bond, and these amines affect the relatively long observed distance in the dipolar-based experiment. Our study shows effectiveness of solid-state NMR for investigation of the ligand-surface interactions of NPs.