Electron spin resonance spectroscopy (ESR) has been used to investigate the electrochemical and photolytic behaviour of particulate C.I. Pigment Red 122. Heterogeneous electrochemical reduction and oxidation of the pigment resulted in different reversible ESR signals with the radical cation giving a signal of ΔHpp = 2.3 G and g-factor of 2.0033 and the radical anion giving ΔHpp = 3.2 G and g-factor 2.0039. On exposure to light the inherent ESR signal, which was determined to be a two-component signal, increased in intensity by a factor of 2.4 but did not change in linewidth or g-factor. This light-induced signal was reversible and decayed to initial levels in the dark. The mechanism of these reactions is discussed. Keywords: ESR, pigment, electrochemistry, photo effects.