Degradation of methyl orange (MO) was carried out by the photo-Fenton process (Fe2+/H2O2/UV) and photo-Fenton-like processes (Fe3+/H2O2/UV, Fe2+/S2O 8 2− /UV, and Fe3+/S2O 8 2− /UV) at the acidic pH of 3 using hydrogen peroxide and ammonium persulfate (APS) as oxidants. Oxidation state of iron had a significant influence on the efficiency of photo-Fenton/photo-Fenton-like processes. It was found that a process with a source of Fe3+ ions as the catalyst showed higher efficiency compared to a process with the Fe2+ ion as the catalyst. H2O2 served as a better oxidant for both oxidation states of iron compared to APS. The lower efficiency of APS is attributed to the generation of excess protons which scavenges the hydroxyl radicals necessary for degradation. Further, the sulfate ions produced from S2O 8 2− form a complex with Fe2+/Fe3+ ions thereby reducing the concentration of free iron ions in the solution. This process can also reduce the concentration of hydroxyl radicals in the solution. Efficiency of the various MO degradation processes follows the order: Fe3+/H2O2/UV, Fe3+/APS/UV, Fe2+/H2O2/UV, Fe2+/APS/UV.