A mesoporous spinel nanofibers consisting of mixed transition-metal oxides (Mn0.6Cu0.4Co2O4; MCCO) were synthesized using a facile electrospinning technique followed by a thermal treatment process. The porous structure results in a high surface area of the MCCO nanofibers, which plays a beneficial role in improving the electrocatalytic properties. By adding nitrogen-doped carbon nanotubes (N-CNT), a composite electrocatalyst MCCO/N-CNT was fabricated. The ORR performances were evaluated in alkaline and neutral media. The results suggest that MCCO/N-CNT hybrid can be used as a promising ORR catalyst for fuel-cell applications.