The long-term property development of fly ash (FA)-based geopolymer (FA−GEO) incorporating industrial solid waste carbide slag (CS) for up to 360 d is still unclear. The objective of this study was to investigate the fresh, physical, and mechanical properties and microstructures of FA−GEO composites with CS and to evaluate the effects of CS when the composites were cured for 360 d. FA−GEO composites with CS were manufactured using FA (as an aluminosilicate precursor), CS (as a calcium additive), NaOH solution (as an alkali activator), and standard sand (as a fine aggregate). The fresh property and long-term physical properties were measured, including fluidity, bulk density, porosity, and drying shrinkage. The flexural and compressive strengths at 60 d and 360 d were tested. Furthermore, the microstructures and gel products were characterized by scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS). The results show that the additional 20.0% CS reduces the fluidity and increases the conductivity of FA−GEO composites. Bulk densities were decreased, porosities were increased, and drying shrinkages were decreased as the CS content was increased from 0.0% to 20.0% at 360 d. Room temperature is a better curing condition to obtain a higher long-term mechanical strength. The addition of 20.0% CS is more beneficial to the improvement of long-term flexural strength and toughness at room temperature. The gel products in CS−FA−GEO with 20.0% CS are mainly determined as the mixtures of sodium aluminosilicate (N−A−S−H) gel and calcium silicate hydration (C−S−H) gel, besides the surficial pan-alkali. The research results provide an experimental basis for the reuse of CS in various scenarios.