The current work aimed to explore the effect of Na/Al ratios of 0.43, 0.53, 0.63, 0.73, 0.83, and 0.93, using NaOH to alter the molar ratio, on the mechanical properties of a geopolymer material, with fixing of the Si/Al molar ratio. While fixing the Na/Al molar ratio, alteration of the Si/Al ratios to 1.7, 1.75, 1.8, 1.85, 1.9, 1.95 was used, with silica fume and sodium silicate as a silica corrector. The influence on the micromorphology and macro-strength of samples was characterized through SEM, EDS, and compressive strength characterization methods. The results show that Si/Al and Na/Al molar ratios play a significant role in the microstructure and mechanical behavior of MK-based geopolymers, and revealed that the optimal molar Si/Al and Na/Al ratios for attaining maximum mechanical strength in geopolymers are 1.9 and 0.73, respectively. Under various Si/Al ratios, the macro-strength of the geopolymer mainly relies on the formation of NASH gel, rather than zeolites or silicate derivatives. The appropriate Na/Al molar ratio can contribute to the geopolymerization, but a ultra-high Na/Al molar ratio caused a high alkali state that destroyed the microstructure of the geopolymers. Regardless of the amount of water contained in the initial geopolymer raw material, the water content of Si/Al = 1.65 and Si/Al = 1.75 after curing for 10 days was almost the same, and the bound water content of the final geopolymer was maintained at about 15%. Structural water exists in geological polymer gels in the form of a chemical structure. It has effects on the structural performance strength, while free water affects the volume stability of the geological polymer. Overall, the current work provides a perspective on the elemental composition analysis, combined with the molecular structure and micromorphology, to explore the mechanical performance of geopolymers.