Many published articles have reported the advantages of coupling photocatalysis and Fenton-based processes for environmental remediation purposes, especially wastewaters treatment, but without providing detailed discussion on how and why the resulting process is better, thus leading to misconception about their synergy. In this work, the context of the water pollution is presented along with the pros and cons of individual photocatalysis and Fenton-based processes. The simultaneous triggering of these two advanced oxidation processes is critically discussed from both performance and mechanism sides since additional effect and synergy are often misunderstood in the literature. Insights into research approaches to clarify the synergistic mechanism between photocatalysis and Fenton-based processes are also provided. One of the key features is to assess the separated contribution of the individual processes and also to elucidate the charge carriers' dynamics at the surface of the catalyst. The aim of this work is to inform scientists about the complexity of simultaneously triggered photocatalysis and Fenton-based processes but also to highlight the potential development of a new generation of catalysts that might be integrated to current wastewater treatment technology to achieve higher efficiency and their implications in the circular economy of water.