Abstract This study investigated the effect of calcium formate (CF) on the strength development and microstructure of the CaO-activated ground granulated blast furnace slag (GGBFS) system. The main activator (i.e., CaO) was fixed at 4 wt%, and the GGBFS was replaced with CF at 0, 1, 3, and 5 wt%. The use of CF significantly increased the strength of the binder system by inducing (1) more dissolution of GGBFS, (2) greater C–S–H formation although when CF was used over a certain limit (i.e., 3 wt%), the formation of C–S–H began to be disturbed, and most importantly, (3) an increase in C2AH8 formation. In this study, although the greater formation of C2AH8 was the main cause of the strength enhancement, the C2AH8 phase also likely increased porosity and reduced strength as it was metastable; thus, strength increasing effect and reducing effect likely offset each other; thus, with increasing CF dosage, when the former was more dominant, the strength was enhanced (e.g., up to 3 wt%), but when the latter was larger, the strength enhancement decreased (e.g., at 5 wt%).