Cobaloximes and their BF<sub>2</sub>-bridged analogues have emerged as promising non-noble metal catalysts for the photocatalytic hydrogen evolution reaction (HER). Herein we report the serendipitous discovery that double complex salts such as [Co(dmgh)<sub>2</sub>py<sub>2</sub>]<sup>+</sup>[Co(dmgBPh<sub>2</sub>)<sub>2</sub>Cl<sub>2</sub>]<sup>-</sup> can be obtained in good yields by treatment of commercially available [Co(dmgh)<sub>2</sub>pyCl] with triarylboranes. A systematic study on the use of such double complex salts and their single salts with simple counterions as photocatalysts revealed HER activities comparable or superior to existing cobaloxime catalysts and suggests ample opportunities for this compound class in catalyst/photosensitizer dyads and immobilized architectures. Preliminary electrochemical and spectroscopic studies indicate that one key advantage of these charged cobalt complexes is that the reduction potentials as well as the electrostatic interaction with charged photosensitizers can be tuned.