To further develop the active site mimics of azadithiolate-bridged [FeFe]-hydrogenases, a series of new diiron azadithiolate complexes [{(μ-SCH2)2N(C6H4CH2CH2OC(O)R)}Fe2(CO)6] (R = CH2C6H4Me-p, 2; C6H5, 3; CH3, 4) bearing bridgehead N-derivation were successfully prepared by facile esterification reaction of parent complex [{(μ-SCH2)2N(C6H4CH2CH2OH)}Fe2(CO)6] (1) and different carboxyl compounds RCO2H in the presence of 4-dimethylaminopyridine (DMAP) as catalyst and dicyclohexylcarbodiimide (DCC) as dehydrating reagent. Complexes 2–4 have been fully characterized by means of elemental analysis, FT-IR and NMR (1H, 13C) spectroscopies, and especially for 2 by X-ray crystallography. Further electrochemical and electrocatalytic properties of target complexes 2–4 and reference analogue 1 were studied and compared in the absence and presence of acetic acid (HOAc) as a proton source by cyclic voltammetry (CV), indicating that they may be considered as the active biomimetic electrocatalysts for proton reduction to hydrogen (H2).