Reported are the synthesis, spectroelectrochemistry and electrocatalytical properties of the bis(2,6-diacetylfurfuryliminepyridine)iron(II) complex, [Fe(dafipy)(2)](2+). The electrochemical behavior observed for this complex in acetonitrile solutions is typically reversible, exhibiting three characteristic waves at 1.40, -0.86 and -1.12 V vs. she, ascribed to the Fe(III/II) and dafipy(0/-1/-2) redox couples, respectively. The electrocatalytical oxidation of organic substrates, such as N,N-dimethylformamide and 4-substituted-1,2-dimethoxybenzenes, in the presence of the [Fe(dafipy)(2)](2+) catalyst proceeds at a lower potential and with great efficiency. The electrocatalytical synthesis of 2,2’-diethyl-4,4’,5,5’-tetramethoxybiphenyl is discussed.