The reactive intermediate radicals formed during an electrochemical reduction of benzyl bromide, benzyl chloride, p-nitrobenzyl chloride, p-methoxybenzyl chloride and p-chlorobenzyl chloride were studied by using the Simultaneous Electrochemical Electron Spin Resonance (SEESR) technique. An attempt was made to elucidate the dehalogenation mechanism of halobenzyl compounds and their derivatives by using a computer simulation of recorded spectra.