Advancements in mine tailings treatment technology have increased the use of superfine tailings, but their extremely fine particle size and high specific surface area limit the performance of superfine tailings cemented paste backfill (STCPB). This study investigates the effects of using superfine cement as a binder to enhance the fluidity, strength, and pore structure of STCPB. The influence of water film thickness (WFT) on STCPB performance is also examined. The results show that the cement-to-tailings ratio (CTR) and solid content (SC) significantly affect the spread diameter (SD) and unconfined compressive strength (UCS), following distinct linear/logarithmic and exponential trends, respectively. WFT has an exponential impact on SD and a non-linear effect on UCS, enhancing strength at low levels (0 μm < WFT < 0.0071 μm) and balancing hydration and flowability at moderate levels (0.0071 μm < WFT < 0.0193 μm) but reducing strength at high levels (WFT > 0.0193 μm). Additionally, superfine cement significantly improves the pore structure of STCPB by reducing porosity and macropore content. These findings provide valuable insights into optimizing STCPB for enhanced performance and sustainability in mine backfilling applications.