Understanding the performance and mechanism of the degradation of various contaminants is essential for the effective design of wastewater treatment systems. This study examined the degradation of 1,4-dichlorobenzene in a photocatalytic system, which embedded TiO2 particles (as a thin film) on alumina balls (as a solid support). Decomposition of the parent compound was assessed by introducing a TiO2 photocatalyst, microwave irradiation, and ultraviolet irradiation jointly or separately (in terms of the system configuration) with and without an adjustment for the microwave intensity, pH, and hydrogen peroxide levels (in terms of the operating conditions) to the photocatalytic system. The results showed that the photocatalytic system adopting multiple processes concomitantly improved the degradation performance of the parent compound that was resistant to the singleunit processes. On the other hand, the decomposition efficiency was increased further with the sophisticated control of the operating conditions, specifically the pH and hydrogen peroxide levels. A dechlorination process as well as substitution and addition reactions involving the hydroxyl radical appeared to occur in the degradation pathway to produce four degradation products from the parent compound. The significance of this study lies in the introduction of a systematic approach to optimizing the operating conditions that facilitate the decomposition efficiency in a given photocatalytic system at no extra cost.