Benzylic nitroalkylation was accomplished by the paired electrolytic reaction of varied benzyl phenyl sulfides and nitroalkanes in the presence of lithium perchlorate. Benzyl cations were generated by anodic oxidation of the sulfides, and the in situ-generated cationic intermediates were trapped by the cathodic-activated nitroalkyl anion to form the desired nitroalkylated products. Furthermore, electrolysis of benzylic dithioacetals efficiently gave the corresponding carbocations to form the desired nitroalkylated compounds.