AbstractMicro/nano lab‐on‐chip power systems with poor energy storage/conversion ability are one of the major obstacles that circumvent the further practical applications of the micro/nano smart devices. In this work, the multilayer Si/TiN/Sb nanorod (NR) arrays composites anodes are successfully fabricated and impressively display improved electrochemical properties in 3D Si‐based lithium/sodium ion microbatteries (L/SIMBs). Both the 3D Si configuration and the efficient TiN interlayer are together responsible for the obtained enhanced cyclability of the Sb nanoelectrode. Moreover, the Li/Na ion storage behaviors are also experimentally investigated from the postmorphology characterizations and further evidences the structure stability of the whole Si/TiN/Sb NRs anodes during the repeated Li/Na ions inserting/de‐inserting process. These multilayer Si/Ti/Sb NR arrays composites should be a promising anode for the 3D Si‐based L/SIMBs.