The oxidation of hexachlorocyclohexane isomers in the aqueous phase (Milli-Q and groundwater) was studied using persulfate activated by ferrioxalate and solar light at circumneutral pH. The experiments were conducted in a solar simulator reactor with local radiation fluxes qw= 1.12·10−7 E cm−2s−1 and in compound parabolic collectors with solar light (qw≈10−7 E cm−2s−1) for 390 min. The effect of activator dosage (18–125 μM ferrioxalate) and persulfate concentration (520–2600 μM) on hexachlorocyclohexane conversion and oxalate and oxidant consumption was analyzed. Conversion of about 95% of β isomer was achieved at 390 min using 1300 μM of initial persulfate and 63 μM of Fe3+ concentration despite this β isomer being the most recalcitrant to oxidation (XHexachlorocyclohexanes=0.98). Dechlorination above 80% was achieved under these conditions, analyzing the chlorides released into the water.The influence of chloride and bicarbonate on hexachlorocyclohexanes degradation was analyzed in milli-Q water and in groundwater. Hexachlorocyclohexane conversion at 390 min decreases from 98% to 83, 75 and 65% in the presence of chloride, bicarbonate or groundwater, respectively. Results obtained with compound parabolic collectors and solar light using 2600 μM Na2S2O8 and 63 μM Fe for removing hexachlorocyclohexanes agreed with those from the solar simulator reactor, supporting using solar light to activate persulfate for sustainable abatement of persistent organic pollutants in aqueous matrixes.