Reducing solid waste emission is the development direction of cleaner production in the future. This paper proposes to use the agricultural solid waste rice husk ash (RHA) as an alternative cementitious material for the underground filling of mines. The pore structure and mechanical properties of cemented paste backfill with different RHA dosages (RCPB) are analyzed. The results reveal that: (1) The pore structure of RCPB is divided into three types: micropores (<0.1 μm), secondary pores (0.1–100 μm), and main pores (>100 μm). The total number of micropores accounts for the largest proportion, followed by secondary pores and main pores. The total volume of secondary pores accounts for the largest proportion, followed by micropores and main pores. (2) The porosity decreases and the UCS increases with the increase of RHA dosage and curing time. The UCS decreases linearly with the increase of RHA dosage. The UCS has a linear negative correlation with porosity. (3) The cracks of RCPB initiated at the yield point, gradually expanded at the peak point, and finally penetrated at the post-peak point. The failure mode of RCPB is mainly a tensile failure, accompanied by a small number of secondary tensile cracks. (4) The hydration products of RCPB are mainly C–S–H and AFt gels. The greater the RHA dosage and CT, the more hydration products, the fewer pores, the greater the strength, and the greater the average gray value. The outcome of this work will afford a new ideas and methods for using solid waste (Rice husk) as backfilling.