Designing and constructing effective and stable photocatalysts is the major challenge in the development of photocatalysis. Herein, we demonstrate a conceptual strategy to effectively improve the charge separation in a ternary material system (CeO2/C/SnS2), by introducing ultrathin carbon layer between CeO2 nanorods and SnS2 particles as a conductive electron transport “highway”. Such ternary CeO2/C/SnS2 gives rise to a largely enhanced photocatalytic removal performance of phenol (100%, 60 min), comparing with CeO2/SnS2 (50%) and CeO2 (20%). Experimental results reveal that carbon layer acts as a high work function, superior electron mobility accepts and enables a fast transportation, accelerating the photocatalytic degradation performance of phenol. Our design introduces material components to provide a dedicated charge-transport pathway, conquering the materials’ intrinsic properties, providing a new perspective for water purity.