5‐hydroxymethylfurfural (5‐HMF) synthesized through glucose conversion requires Lewis acid (L) site for isomerization and Brønsted acid (B) site for dehydration. The objective of this work is to investigate the influence of the metal type of Al‐SBA‐15‐supported phosphates of Cr, Zr, Nb, Sr, and Sn on glucose conversion to 5‐HMF in a NaCl‐H2O/n‐butanol biphasic solvent system. The structural and acid property of all supported metal phosphate samples were fully verified by several spectroscopic methods. Among those catalysts, CrPO/Al‐SBA‐15 provided the best performance with the highest glucose conversion and 5‐HMF yield, corresponding to the highest total acidity of 0.65 mmol/g and optimal L/B ratio of 1.88. For CrPO/Al‐SBA‐15, another critical parameter is the phosphate‐to‐chromium ratio. Moreover, DFT simulation of glucose conversion to 5‐HMF on the surface of the optimized chromium phosphate structure reveals three steps of fructose dehydration on the Brønsted acid site. Finally, the optimum reaction condition, reusability, and leaching test of the best catalyst were determined. CrPO/Al‐SBA‐15 is a promising catalyst for glucose conversion to high‐value‐added chemicals in future biorefinery production.