Nitric oxide (NO) is a key signaling molecule with important functions in various physiological and pathological processes such as neurotransmission, cardiovascular function regulation and immune response. NO can bind with metal ions to form stable complexes, which becomes a promising candidate for the physiologically targeted delivery of NO. Photo-controlled NO donors based on Ru and Fe complexes were synthesized. The photodynamic reactions of metal nitrosyl complexes were investigated with time-resolved FT-IR and EPR spectroscopies, and the released NO was successfully imaged in living cells using a NO selective fluorescent probe. Moreover, the crystal structure and molecular docking analyses revealed that the complexes bind with human serum albumin (HSA), HSA could be a nano-delivery vehicel for these complexes. This study provides insight into the potential biological and pharmaceutical applications for these metal nitrosyl complexes.