To address the bottlenecks of sluggish sodium-ion transfer processes, the electrode materials of sodium-ion battery (SIB) are always designed from the viewpoints of sodium-ion diffusion kinetics or reaction thermodynamics for high-performance sodium storage. Herein, starting with spongiform TiO2/C composite derived from zinc alginate, a NH4Cl-assisted annealing strategy is developed to prepare chlorine-doped spongiform TiO2/C composite (ZATC-Cl). Acting as the anode of SIBs, the obtained ZATC-Cl delivers excellent sodium storage performance with a high reversible capacity of 352.4 mAh g−1 at 50 mA g−1, a superior rate capability of 246.8 mAh g−1 at 2 A g−1 and a considerable high-rate cycling performance of 248.5 mAh g−1 at 2 A g−1 for 1000 cycles. It is believed that the unique spongiform structure and ultra-small sized TiO2 particles in ZATC-Cl can achieve fast sodium-ion insertion/extraction, realizing rapid sodium-ion diffusion kinetics. Moreover, as well evidenced by experiment results and theoretical calculations, the Cl dopants introduced in ZATC-Cl can provide more active sites for robust sodium-ion chemical adsorption, optimizing sodium-ion reaction thermodynamics. This study demonstrates an alternative approach to improve the sodium storage capability of TiO2 anodes by the synergistically engineering the morphological and structural properties and manipulating the surface active sites, from both kinetic and thermodynamic viewpoints of sodium storage processes.