Oxide anodes require a robust structure to enhance cyclability during lithium storage processes, and structural engineering plays a crucial role in achieving this goal. In this work, the SnO2/TiO2 heterojunction nanofibers with core–shell structures is carefully engineered by electrospinning and following annealing processes. These nanofibers exhibit exceptional cyclability and rate performance at a condition of Sn/Ti molar ratio of 1:2, with a reasonable reversible capacity of 650 mAh g−1 at 0.2 A g−1, a notable rate capacity of 326 mAh g−1 at 2 A g−1 and enhanced cyclability of 303 mAh g−1 (2 A g−1) over 2000 cycles. The performance enhancement can be attributed to the distinctive core–shell structure, which provides effective volume buffering, and the heterojunction introduces internal electric fields, enhancing charge transfer kinetics and reducing electric resistance. The study reveals that systematically designed SnO2/TiO2 nanocomposites exhibit enhanced electrochemical performance, showing promise for lithium storage applications.