NiO-In2O3 composite nanofibers were fabricated by the electrospinning method. p-n heterojunctions were successfully formed in the NiO-In2O3 composite nanofibers. Surface absorbed oxygen content and BET surface area increased by addition of NiO. The composite nanofibers showed higher sensing performance than pure In2O3 fibers. The sensing enhancement mechanism of the NiO-In2O3 composite nanofibers was proposed.