Cu-Rh bimetallic single-phase spinel oxide nanofibers were synthesized via electrospinning followed by post-annealing in precisely controlled oxidative environments. By systematically tuning the O2 concentration in the He carrier gas flow during the annealing process, the optimal atmosphere was identified to produce phase-pure CuRh2O4. The as-prepared CuRh2O4 nanofibers exhibited excellent electrocatalytic performance toward the oxygen evolution reaction in 1.0 M NaOH (aq), highlighting the importance of atmosphere-controlled thermal treatment for engineering high-activity spinel oxide electrocatalysts.