Octachlorodipropyl ether (OCDPE) is a chloroalkyl ether widely used as an insecticide synergist, which was considered as a widespread persistent pollutant. Photodegradation kinetics of OCDPE in selected organic solvents was studied using the high-performance thin-layer chromatography (HPTLC) method in this paper. The results showed that photochemical reaction of OCDPE in organic solvents such as n-hexane, methanol, acetonitrile, and acetone under the irradiation of ultraviolet light could well be described by the first-order kinetic equation. The photodegradation rate constants of OCDPE in methanol, acetone, acetonitrile, and n-hexane were 0.3310, 0.2382, 0.0287, and 0.0276 h−1, and the corresponding half-lives were 2.09, 2.91, 24.1, and 25.1 h, respectively. Photodegradation kinetics of OCDPE under sunlight was slower than UV light, the half-lives of which were 8.87 and 2.09 h, respectively. The main photodegradation products of OCDPE in acetone and methanol under UV light were detected by HPTLC, which included product 01 (RF = 0.19) and product 02 (RF = 0.82). Identification of the main photodegradation products of OCDPE requires further studies.