The electron paramagnetic resonance (EPR) parameters of a free radical depend strongly on its microenvironment and stable radicals can be used as reporter molecules for the EPR probing of various chemical and biological systems. Nowadays, nitroxides and trityl radicals are the most important spin labels or spin probes and their use in various applications, spin labeling, spin trapping, oximetry, pH measurement, evaluation of redox status, interactions in supramolecular systems, and so on, are examined.