Benign design of alkali-activated slag/FA geopolymer paste has attracted increasing attention for optimizing its service performance. Therefore, the replacement of fly ash (FA) with 10 wt% silica fume (SF) is investigated by mechanical strength after freeze–thawing cycles and microstructure characterization. The results show that an appropriate dosage (30 wt%) of slag is necessary to prepare heat-free curing alkali-activated slag/FA geopolymer paste with excellent mechanical performance. The SF/slag/FA (SF:slag:FA = 10:30:60, wt%) geopolymer paste exerts an enhanced compressive and flexural strength of 95.2 and 3.2 MPa, respectively. Meanwhile, the doped 10 wt% SF facilitates the propagation of (N, C)-A-S-H chains, rather than the formation of C-S-H gels. It is evidenced by the absent exothermic peak at about 861 °C from the differential scanning calorimetry (DSC) curves. The pores volume and tortuosity also rise for the pore diameter < 20 nm from mercury intrusion porosimeter (MIP) results, corresponding to an improved freezing–thawing resistance with the residual compressive strength of 52.8 MPa and the weight loss of 10.5% after 300 freeze–thawing cycles. It explores a cost-effective and benign facile approach to designing heat-free curing alkali-activated slag/FA geopolymer paste with good freezing–thawing resistance.