SAPO-37 molecular sieve, characterized by its three-dimensional 12-membered-ring FAU structure, has drawn wide attention due to its unique properties and catalytic potential. However, its susceptibility to framework collapse under low-temperature and humid conditions hinders practical applications, affecting both the reaction performance and sample storage. To tackle this, we utilized aluminum phosphate as a precursor for synthesizing SAPO-37, aiming to modify Si incorporation mechanisms and improve P and Al environments. Solid NMR spectroscopy combined with other techniques proves that the resulting SAPO-37-AP has enriched silicon islands, leading to reduced water adsorption, more reversible structural change, and significantly enhanced stability after low-temperature vapor treatment compared to conventional SAPO-37. Remarkably, SAPO-37-AP, after water vapor treatment, still exhibits superior performance in the liquid-phase Beckmann rearrangement reaction. This approach enhances stability, reduces templating agent amounts, and improves the solid product yield, offering promising practical applications.