Micro/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. Multilayer Si/TiN/Sb nanorod arrays composites anodes are successfully fabricated using the semiconductor micromachining technology. The introduction of the efficient TiN interlayer combined with the patterned Si substrate and the Sb active material impressively display superior electrochemical performance when applied in 3D Si‐based lithium/sodium ion microbatteries.