In this study, carbon-quantum-dot (CQD)-decorated TiO2 was prepared using an ultrasonic doping method and applied in the photocatalytic degradation of naphthalene under sunlight irradiation. The CQDs were synthesized from a typical macroalgae via diluted sulfuric acid pretreatment and hydrothermal synthesis using an optimal design, i.e., 3 wt% and 200 °C, respectively. The CQD/TiO2 composite remarkably enhanced the photocatalytic activity. The degradation of naphthalene under a visible light environment indicated that there is a synergistic mechanism between the CQDs and TiO2, in which the generation of reactive oxygen species is significantly triggered; in addition, the N that originated from the macroalgae accelerated the photocatalytic efficiency. Kinetic analysis showed that the photocatalytic behavior of the CQD/TiO2 composite followed a pseudo-first-order equation. Consequently, our combined experimental approach not only provides a facile pretreatment process for bio-CQDs synthesis, but also delivers a suitable TiO2 photocatalyst for the visible environment along with critical insights into the development of harmful macroalgae resources.