This study focused on investigating the effect of reaction conditions (catalyst and H2O2 dosage, light source under different pH) and liquid property on degradation of phenol over RGO/alpha-FeOOH supported on Al-MCM catalyst in heterogeneous photo-Fenton system. Batch experiments were conducted under specific operating conditions. It was found that with the increase of catalyst and H2O2 dosage, the phenol and COD removal efficiency went up to reach a maximum (at Cata/H2O2 mass ratio was 1.471) and then decreased. The reactions all fitted pseudo first order model. The phenol were degraded apparently by RGO/alpha-FeOOH-Al-MCM catalyst at different light source irradition or not when pHs ranged from 4.0 to 8.0. The solar irradiation not only dramatically accelerated the rate of Fenton-based reactions, but also extended the operating pH for the Fenton reaction (from 4.0 to 8.0). Higher initial phenol concentrations inhibited the rate of phenol degradation although actual phenol removal amount increased, which may be due to the fact that more intermediates produced at higher phenol concentration competed with phenol for the active sites. The addition of anions (Cl-, SO42-, NO3-, HCO3-, HPO42-), small molecule organic acids (CA, OA, TA) and natural organic matter (HA, FA) caused inhibition effect on phenol degradation.