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The Development of transformative technology capable of producing inexpensive superior lithium electroactive anode material with low volume changes and stable performance on cycling is an important step on the path to advanced application of lithium ion batteries (LIBs). In this work, a new synthesis strategy for hybrid SnO2-Co3O4 nanotubes, based on electrospun polyvinylpyrrolidone (PVP) fibers with co-embedded metal precursors is explored. This low cost, template-free, Kirkendall effect-derived process first yields phase-separated core-sheath PVP/SnO2-Co3O4 composites, creating highly uniform and well-dispersed nanotubes via self-assembly accompanying gradual PVP combustion. Control experiments show that the heat-treatment atmosphere is the key for the in situ growing in a large yield. On account of the great buffering capability in hierarchical porous architecture, synergistic effect of active multi-components and the present interfacial Co nanophase, the proposed tubular hybrids possess enhanced cyclic stability and lithium storage capacity as anodes with retained capacity as high as 873 mAh g−1 even after 200 cycles at 100 mA g−1. The protocol paves the way for rational design of hollow hybrid nanotubes with wide applications.