SAPO-34 is a crystalline microporous material, the characteristics of which are greatly influenced by synthetic parameters, especially the silica precursors and templates. In this study, the combination of templates and silica sources was optimized to obtain SAPO-34 phases in the purest form. The physicochemical properties of the thus-synthesized catalysts were characterized, and the Si environment in the SAPO-34 framework was analyzed. The catalytic performance in biomass gasification was investigated in a fixed-bed flow reactor. SAPO-34 synthesized with triethylamine/morpholine/tetraethylammonium hydroxide templates exhibited the highest total acidity, the smallest particle size, and high surface area, and produced a large amount of light hydrocarbons in biomass gasification.