•Inexpensive Al2O3/C3N4 hybrid with high visible light activity is firstly reported.•Defect sites existed in amorphous Al2O3 are excellent electron acceptors.•G-C3N4 is surface modified by NH4OH to enhance hydroxyl groups.•The role of hydroxyl in the formation process of g-C3N4-based hybrids is discussed.•The reason responsible for the surface positive charges of Al2O3 is presented. Novel Al2O3/g-C3N4 heterojunction photocatalysts were fabricated through ultrasonic dispersion method. Al2O3, obtained via solution combustion, contained amorphous ingredient with lots of defect sites and was used as active component for transferring photo-induced electrons of g-C3N4. G-C3N4 was grafted surface hydroxyl groups in the presence of ammonia aqueous solution to combine with Al2O3 possessing positive charges via hydrogen bond. The XRD, SEM, element map, TEM, HRTEM, FT-IR, and XPS results indicate that these synthesized materials are two-phase hybrids of Al2O3 and g-C3N4 with interaction. The photocatalytic results for the degradation of rhodamine B (RhB) indicate that the most active heterojunction proportion is 60wt.% g-C3N4:40wt.% Al2O3, the visible light photocatalytic activity of which is 3.8 times that of a mechanical mixture. The enhanced performance is attributed to the high separation efficiency of photo-induced electrons from the LUMO of g-C3N4 injected into the defect sites of Al2O3, which is verified by photoluminescence spectroscopy (PL) and surface photovoltage (SPV) measurements. The electron paramagnetic resonance (EPR) signals and radical scavengers trapping experiments reveal holes (h+) and superoxide anion radical (O2−) are the main active species responsible for the degradation of RhB.