The homodinuclear Co-II helicate complex [Co-II(DQPD)](2) (1) was prepared by treating [Co(H2O)(6)](ClO4)(2) with the deprotonated form of the ligand N-2,N-6-bis(quinolin-8-yl)pyridine-2,6-dicarboxamide (DQPDH(2)). Complex 1 represents a discrete homodinuclear helicate complex with two Co-II centers having a distorted-octahedral geometry through an unprecedented pyridine bridge. Complex 1, upon treatment with H2O2, undergoes oxidation at one of the Co-II centers followed by a structural deformation to generate the mixed-valence complex [(CoCoII)-Co-III(DQPD)(2)](ClO4) (2 center dot ClO4). In complex 2, the bridging through the central pyridine collapses along with the formation of Co(III) octahedral and Co(II) tetrahedral environments. Complexes 1 and 2 interconvert to one another. The effective magnetic moments for complexes 1 and 2 are respectively 5.88 and 4.30 mu(B). Complexes 1 and 2 have been employed for electrocatalytic proton reduction using AcOH as the proton source in 95/5 (v/v) DMF/H2O. A TOF of 30000 mmol of H-2 h(-1) (mol of 1)(-1) at a potential of -1.7 V vs SCE was achieved. A resting-state analysis has been carried out to support the mechanism for the catalytic proton reduction.