Organophosphorus phosphate(OPEs)and Cr(VI) are common compound pollutants in electronic waste dismantling area. Simultaneous photooxidation of tris (2-chloroethyl) phosphate (TCEP) and photoreduction of Cr(VI) by Fe(III) in aqueous solution were studied under 300 W mercury lamp (λ = 365 nm). The effects of the initial concentrations of Fe(III), Cr(VI), and TCEP were investigated. The regeneration of Fe(III)/Fe(II) redox cycle in UV/Fe (III) was studied. The applicability of UV/Fe(III) to degradation of other OPEs was proved. The results showed that photocatalytic degradation of TCEP and reduction of Cr(VI) occurred simultaneously in UV/Fe (III) system. The increased Fe (III) initial concentration was beneficial to the photocatalytic reduction of Cr(VI) and the oxidation of TCEP. The reduction of Cr(VI) increased with the increasing TCEP initial concentration. However, the Cr(VI) concentrations had no significant effect on TCEP degradation. TCEP can be degraded completely and Cr(VI) can be reduced in five cycles. Similar photocatalysis effects were observed for other organic phosphates (OPEs). As a homogeneous photocatalytic method, UV/Fe(III) can solve the compound pollution containing OPEs and Cr(VI) at the same time.