Chemical and biological functions of hemoprotein nitrosyl complexes as well as their photolysis products are discussed in this review. Chemical properties of nitric oxide are discussed, and major chemical reactions such as interaction with thiols, free radicals, and transition metals are considered. Specific attention is paid to the generation of hemoprotein nitrosyl complexes. The mechanisms of nitric oxide reactions with hemoglobin and cytochrome c and physicochemical properties of their nitrosyl complexes are discussed. A review of photochemical reactions of nitrosyl complexes with various ligands is given. Finally, we observe physiological effects of visible radiation on hemoprotein nitrosyl complexes: smooth muscle relaxation and reactivation of mitochondrial respiration.