Nickel(I) salen, electrogenerated from nickel(II) salen by means of controlled-potential electrolysis at a carbon cathode in dimethylformamide containing tetramethylammonium perchlorate, catalytically reduces alpha,omega-dihaloalkanes via a one-electron process that yields a radical intermediate. From 1-bromo-4-chioro- and 1-chloro-4-iodobutane, we have obtained 1,8-dichlorooctane as the principal product (> 88%) along with small amounts of 1-chlorobutane (7%-10%) and 4-chloro-1-butene (2%). Catalytic reduction of 1-bromo-5-chloro- and 1-chloro-5-iodopentane affords 1,10-dichlorodecane in high yield (79%-86%) as well as smaller quantities of 1-chloropentane (11%-18%) and 5-chloro-1-pentene (2%-3%). When 1-bromo-6-chloro- and 1-chloro-6-iodohexane are catalytically reduced with nickel(I) salen, 1,12-dichlorododecane is formed in excellent yield (91%-92%), and 1-chlorohexane (9%) and 6-chloro-1-hexene (2%) are minor products.