Emission and capture rates describing the optical and thermal transitions at the ’’Cu‐red’’ center in ZnSe have been investigated using a modified photocapacitance technique. By keeping the depletion region of a Schottky diode constant during the measurements of transients highly compensated samples could be used, resulting in larger signals than previously possible. This permitted optical‐emission rates for both electrons and holes to be measured with higher accuracy and in a broader temperature region than in previous investigations. The capture cross section of electrons &sgr;nwas determined in the temperature range 77–200 K. &sgr;nincreases with decreasing temperature and has a value of 1.4×10−19cm2at 77 K.