ZnSe diodes grown on (100) GaAs substrates by molecular beam epitaxy were investigated using cathodoluminesence (CL) measurements at sample temperatures between 50 and 300 K. The CL line scans at different photon energies were performed on cleaved p–n junctions at 50 and 300 K, respectively. Taking into account surface recombination, carrier generation volume, carrier diffusion and internal built-in electric field and related carrier drift, the CL measurements from cleaved p–n junctions could be qualitatively explained. The charge depletion layer has a strong influence on the CL measurements. The calculated charge depletion width is in good agreement with CL measurements. The experimental data from the spatially resolved CL on the cleaved ZnSe diodes revealed important information of the carrier dynamics and recombination processes in these devices.