Carbon materials as promising anode for potassium ion batteries (PIBs) suffer from low rate performance, which is attributed to sluggish K+ transport stemming from limited carbon interspace and elusive solvent effect. Herein, interspace design and solvent effect are investigated to resolve this issue. Through an innovative salt template assisted molten sulfur method, large hollow pores, massive micropores and expanded interlayer spacing are integrated in a high sulfur-doped porous carbon (S-PC), showing obviously higher rate capability (351.5 and 122.3 mA h g−1 at 0.1 and 20 A g−1, respectively) than pristine porous carbon (PC). Furthermore, the S-PC exhibits significantly-higher rate performance in ester-based electrolyte (1 M KFSI/EC + DEC) than in ether one (1 M KFSI/DME). Kinetic study demonstrates advantage of interspace design and ester-based electrolyte on promoting faster K+ transport. The explicit solvent effect on S-PC is further examined by XPS and HRTEM analyses, revealing a desirable inorganic KF-salt-dominated, thin solid electrolyte interface (SEI) layer in ester-based electrolyte. This work opens new avenues for precise design of advanced carbon materials for high-rate PIBs.