A superior heterojunction of HC-ZnBi-LDO was synthesized in two steps, namely hydrothermal carbonization, followed by co-precipitation. The 2% HC-ZnBi-LDO heterojunction photocatalysts could degrade over 90.8% of 30 mg/L 2,4-dichlorophenoxyacetic acid (2,4-D) using 1.0 g/L of the catalyst after 135 min of visible light exposure at pH 4. The activity of 2% HC-ZnO-LDO was remarkably stable. Approximately 86.4–90.8% of 30 mg/L 2,4-D was degraded, and more than 79–86.4% of TOC was mineralized by 2% HC-ZnBi-LDO at pH 4 after 135 min of visible light exposure during four consecutive cycles. The rapid separation and migration of charge carriers at the interfaces between HC and ZnBi-LDO were achieved within 2% HC-ZnBi-LDO. Moreover, the electron acceptor characteristic of HC in 2% HC-ZnBi-LDO caused the recombination of charge carriers to decrease significantly, thus generating more reactive radicals, such as hydroxyl radicals (OH●) and superoxide radicals (O2●−). These results demonstrate that the novel 2% HC-ZnBi-LDO is a superior photocatalyst for the remediation of hazardous organic pollutants.