In order to improve the aggregation phenomenon of metal phthalocyanines and enhance their photocatalytic activity, MIL-53(Al) with flexible frame and large pore structure was selected as the carrier, and carboxyl substituted metal phthalocyanines (MTcPc, M=Mn, Fe, Co, Ni, Cu, Zn) were loaded on the surface of MIL-53(Al) by hydrothermal method. MTcPc/MIL-53(Al) composite material with adsorption-photocatalytic oxidation desulfurization performance was prepared. Its morphology, structure and element distribution were characterized by SEM, XRD, FTIR, UV-Vis and XPS, and thiophene/n-octane was used as simulated fuel at room temperature and pressure with oxygen as oxidant. The desulfurization performance of MnTcPc/MIL-53(Al) photocatalytic oxidation was tested. The results showed that the phthalocyanine molecules were evenly dispersed on the carrier MIL-53(Al) in an ordered crystalline form, and the agglomeration problem was significantly improved. The planar conjugated structure of the phthalocyanine molecules had an obvious induction effect on the growth of MIL-53(Al) crystals in a specific direction. The Q-band of MTcPc/MIL-53(Al) has a certain degree of redshift, which extends the optical response range. MnTcPc/MIL-53(Al) showed the best photocatalytic desulfurization performance. After 150 min of catalytic reaction, the thiophene conversion rate was 100%. After five cycles of use, the thiophene conversion rate decreased to 93.01%.Moreover, the breathing effect of MIL-53(Al) promoted the enrichment of thiophene molecules and molecular oxygen on the catalyst surface, which was conducive to the formation of active intermediate MIL-53(Al)/MTcPc-1O2 to improve the photocatalytic desulfurization properties of thiophene. Mechanistic studies revealed that the conjugation structure and central ion configuration of metal phthalocyanine strongly affected the oxidative desulfurization properties of MIL-53(Al)/MTcPc.