Nickel bis(dithiolene) reversibly binds olefins via a known interligand binding mechanism, but the complex has limited practical use, due to a competitive intraligand addition which results in decomposition. The present work examines an alternative nickel-based complex that eliminates the decomposition route. Specifically, we have examined the olefin binding processes of nickel bis(diselenolene) complexes using modem density functional theory. Both the inter- and intraligand adducts of the nickel bis(diselenolenes) are thermodynamically more stable than their dithiolene analogues. We have predicted that nickel bis(diselenolene) complexes do not decompose after the intraligand addition, and that the overall activation energies for the kinetically accessible products are quite small. In short, our computational work predicts that nickel bis(diselenolene) complexes are better electrocatalysts for olefin purification than the previous candidates, superior to the previously studied nickel bis(dithiolene) complexes.