A new material for both magnetic coupling and electrocatalytic hydrogen generation based on a copper complex,[(HL)CuCl-CuCl(HL)]HCl 1 is prepared by the reaction of 2-(pyridylmethyl)amino-N,N-bis(2-methylene-4,6-difluorophenol)(H_2L) and CuCl_2·2H_2O.In solid,complex 1 is built from two copper units([(HL)CuCl]),and exhibits an antiferromagnetic exchange interaction between copper(Ⅱ) ions(J=-160cm~(-1)).In liquid,1 can electrocatalyze hydrogen generation both from acetic acid with a turnover frequency(TOF) of 16.3 moles of hydrogen per mole of catalyst per hour at an overpotential(OP)of 941.6 mV(in DMF),and a neutral buffer with a TOF of 1415.6 moles of hydrogen per mole of catalyst per hour at an OP of 787.6 mV. A new material for both magnetic coupling and electrocatalytic hydrogen generation based on a copper complex, [(HL) CuCl-CuCl (HL)] HCl 1 is prepared by the reaction of 2- (pyridylmethyl) amino- complex and is formed from two copper units ([(HL) CuCl]), and exhibits an antiferromagnetic exchange interaction between copper (Ⅱ) ions (H_2L) and CuCl_2 · 2H_2O.In solid, J = -160 cm -1) In liquid, 1 can electrocatalyze hydrogen generation both from acetic acid with a frequency of 1 (TOF) of 16.3 moles of hydrogen per mole of catalyst per hour at an overpotential (OP) of 941.6 mV (in DMF), and a neutral buffer with a TOF of 1415.6 moles of hydrogen per mole of catalyst per hour at an OP of 787.6 mV.