This article investigated the potential of fly ash (FA)/blast furnace slag- (BFS-) based geopolymer as a novel backfilling material. The effects of NaOH concentration and FA/BFS mass ratio were explored through XRD, FTIR, and TG-DTG analyses. The results indicated that the reaction products and strengths of geopolymer depended on the NaOH concentration and types of source materials. Slump, final setting time, and setting ratio increased as a function of FA content. However, the increase in FA content reduced the compressive strength and microstructure of the backfilling material (BM) due to the lower reactivity than BFS. Microstructure analysis reveals that the matrix tends to be denser with the BFS content and NaOH concentration increase.