SnO2 nanoparticles uniformly decorated polypyrrole (PPy) nanowires are synthesized by a facile two-step electrochemical reaction method: electropolymerization and electrodeposition. The nanostructured SnO2–PPy hybrids show porous reticular morphology and homogenous distributions. The reticular SnO2–PPy nanowires can increase the electrode/electrolyte interface and accommodate the volume variation of SnO2. When applied as anode materials for lithium ion batteries, the unique nanostructured hybrids deliver meaningfully improved Li+ storage performance with the first reversible capacity of 690 mAh g−1. This facile synthesis procedure can also be simply grafted to other inorganic–organic hybrid composites.