Silicon-air batteries (SABs) have become promising candidates for energy conversion and storage devices due to their high theoretical energy density, cost-effectiveness, and inherent safety. However, the slow kinetics of the 4e− transfer in the oxygen reduction reaction (ORR) at the cathode during discharge, coupled with severe polarization, reduces the battery’s capacity and hinders the development of silicon-air batteries. The cathodes of currently developed SABs primarily rely on commercial Pt/C and MnO2, with limited research on low-cost, efficient, and stable air cathodes for SABs. To address this issue, we synthesized nitrogen-doped carbon nanotubes containing FeMn alloy particles (FeMn@NCNTs) as cathode ORR catalysts using a simple high-temperature pyrolysis method combined with chemical vapor deposition. In an alkaline medium, the catalyst’s half-wave potential (E1/2) reached 0.83 V. Moreover, the FeMn@NCNTs air cathode exhibited excellent compatibility with the silicon anode, and the constructed aqueous silicon-air battery demonstrated a high specific capacity (165 Ah kg−1) and power density (3.69 mW cm−2). Additionally, the quasi-solid-state SABs constructed with FeMn@NCNTs showed stable operation over a wide temperature range, providing a new solution for the development of low-cost, efficient silicon-air batteries suitable for a wide range of applications.