Selenium (Se) is a naturally occurring metalloid that has been widely sourced for health care, clean energy technology development, and agricultural activities. These activities have accelerated Se release into the aquatic environment, urging engineered solutions to mitigate aquatic Se pollution and their ecological impact. Our lab previously demonstrated a direct electrochemical reduction approach to convert 97% of soluble selenite into elemental Se(0) on a gold cathode. This study builds upon our prior success in selenite separation to further explore alternative cathode materials to gold. Six economically competitive materials (Ni, graphite, Cu, Fe, stainless steel, and Ti) were evaluated for key performance parameters, including Se removal efficiency, Faradaic efficiency, energy consumption, and electrode durability. Preliminary cyclic voltammetry scans revealed that Ni and graphite could sustain Se(IV)/Se(0) reduction in diluted water matrices within their electrochemical window. The subsequent 24-h chronoamperometry (CA) test demonstrated 67% selenite removal using a Ni cathode, while graphite offered a better removal efficiency (92%). Separated selenite ions were primarily plated as elemental Se(0) on the cathode surface (Ni & graphite) or within the electrode structure (graphite). While graphite has better selenite removal than Ni, it demands more energy input and has lower Faradaic efficiency (C-3.7% vs. Ni-12.7%). Switching from a CA mode to a chronopotentiometry (CP) mode did not significantly impact selenite removal performance, and the energy consumption was increased by 15%. Continued exfoliation is observed on the graphite electrode surface, potentially due to the expansion of inner gas bubbles and the lattice destruction caused by Se(0) insertion. Our results suggest graphite offers comparable selenite separation performance to a gold cathode. Still, electrode exfoliation and higher energy input due to parasitic reactions must be appropriately addressed in future research efforts.