In this work, the PIL (poly ionic liquid)@TiO2 composite was designed with two polymerized ionic liquid concentrations (low and high) and evaluated for pollutant degradation activity for benzene and toluene. The results showed that PIL (low)@TiO2 composite was more active than PIL (high)@TiO2 composites. The photodegradation rate of benzene and toluene pollutants by PIL (low)@TiO2 and PIL (high)@TiO2 composites was obtained as 86% and 74%, and 59% and 46%, respectively, under optimized conditions. The bandgap of TiO2 was markedly lowered (3.2 eV to 2.2 eV) due to the formation of PIL (low)@TiO2 composite. Besides, graphene oxide (GO) was used to grow the nano-photocatalysts’ specific surface area. The as-synthesized PIL (low)@TiO2@GO composite showed higher efficiency for benzene and toluene degradation which corresponds to 91% and 83%, respectively. The resultant novel hybrid photocatalyst (PIL@TiO2/m-GO) was prepared and appropriately characterized for their microstructural, morphology, and catalytic properties. Among the studied photocatalysts, the PIL (low)@TiO2@m-GO composite exhibits the highest activity in the degradation of benzene (97%) and toluene (97%). The ultimate bandgap of the composite reached 2.1 eV. Our results showed that the as-prepared composites hold an essential role for future considerations over organic pollutants.