Hazardous chemicals are transported on rail and road networks. In the case of accidental spillage or terror attack, civilian and military first responders must approach the scene equipped with appropriate personal protective equipment. The plausible manufacturing of chemical protective polymer material, from photocatalyst anatase titanium dioxide (TiO₂) doped low-density polyethylene (LDPE), for cost-effective durable lightweight protective garments against toxic chemicals such as 2-chloroethyl ethyl sulphide (CEES) was investigated. The photocatalytic effects on the physico-chemical properties, before and after ultraviolet (UV) light exposure were evaluated. TiO₂ (0, 5, 10, 15% wt) doped LDPE films were extruded and characterized by SEM-EDX, TEM, tensile tester, DSC-TGA and permeation studies before and after exposure to UV light, respectively. Results revealed that tensile strength and thermal analysis showed an increasing shift, whilst CEES permeation times responded oppositely with a significant decrease from 127 min to 84 min due to the degradation of the polymer matrix for neat LDPE, before and after UV exposure. The TiO₂-doped films showed an increasing shift in results obtained for physical properties as the doping concentration increased, before and after UV exposure. Relating to chemical properties, the trend was the inverse of the physical properties. The 15% TiO₂-doped film showed improved permeation times only when the photocatalytic TiO₂ was activated. However, 5% TiO₂-doped film exceptionally maintained better permeation times before and after UV exposure demonstrating better resistance against CEES permeation.