Several advanced oxidation processes (AOPs) including photocatalytic processes were studied for effective treatment of complex model wastewater containing a wide variety of VOCs. The studies revealed synergistic effects of TiO2 based processes for improved degradation of the VOCs. A peroxone combined with TiO2/UV system (TiO2/UV/O-3/H2O2) with a ratio between the oxygen source from the oxidant to chemical oxygen demand (COD) of the model wastewater (r(ox)) of 0.5 and 100 mgTiO(2)/L was the optimal process. TiO2 revealed to be economically reasonable to be used in TiO2/UV/H2O2 and TiO2/UV/O-3/H2O2 photocatalytic technologies for efficient and fast (100 min) degradation of VOCs with significantly low amounts of chemicals. Developed system provide high effectiveness with low treatment cost, which in case of most VOCs studied provide satisfactory effects in 15 min. of treatment process with 4 $/m(3) of process costs. The technologies are promising in degradation and purification in several types of industrial effluents with a high VOCs content.