The temperature dependence of the electron capture process was investigated for a series of divalent sulfur compounds. The electron affinity and/or the activation energy for the electron capture reaction were calculated for individual compounds by plotting In KT3/2vs. 1/T, where K is the electron capture coefficient and T is the absolute temperature in the detector. The correlation between these values and chemical structure was discussed by means of 3d orbital resonance of the sulfur atom.