The static compaction technique emphasizes the reduced activator dosage required to develop geopolymers. Therefore, it is crucial to comprehend the optimal alkaline activator concentration for blending low-calcium precursor (fly ash) with high-calcium precursor (GGBS) to produce geopolymer blocks. This work was designed to optimize structural blocks’ compressive strength and durability. In experimentation, fly ash (FA) and slag (GGBS) proportions were initially investigated under NaOH solution with varying molarity (8–12) and curing conditions to develop a load-bearing structural block. Subsequently, the durability of the optimized block was evaluated over 56 days through subjection to sulfate and acidic solutions, with efflorescence monitored over the same period. The results reveal that the structural block comprised of 100% FA exhibits the highest compressive strength and lowest bulk density. Conversely, the block incorporating 25% slag that underwent hot curing demonstrates a remarkable 305% strength increase compared to ambient curing. Considering the physico-mechanical performance, the 100% FA block was chosen for durability investigation. The findings indicate a substantial strength loss exceeding 40% after exposure to sulfate and acidic environments over 56 days, coupled with pronounced efflorescence. Catastrophic failure occurs in all cases due to significant strength deterioration. The FTIR spectrum revealed the shifting of the wavenumber to a higher value and verified the depolymerization and leaching of alumina under acidic exposure. However, the developed geopolymer blocks demonstrate superior sustainability and feasibility compared to conventional fired clay bricks and cement-based FA bricks. Despite slightly higher costs, these blocks exhibit greater strength than their counterparts after enduring severe exposures.