The application of spin-trapping technique to detect short-lived paramagnetic species formed during photochemical reactions of coordination compounds is reviewed. Interference of radical recombinations by scavenging action of spin traps has been pointed out to be important at high spin-trap concentrations only. Due to only a limited extent of side reactions, nitrosodurene and phenyl N-tert-butyl nitrone were found to be excellent spin traps for the study of photoreactions of metal complexes in nonpolar solutions, whereas 5,5-dimethyl pyrroline-1-oxide is recommended for aqueous solutions. Using these spin traps, both organic and inorganic radicals, e.g. H, Cl, N3, CN, OH, O2−, as well as solvated electrons and metal-centered free radicals have been detected during the photolysis of coordination compounds. The detection of singlet oxygen by reaction with 2,2,6,6-tetramethyl piperidine is briefly discussed.