Recycling industrial solid waste not only saves resources but also eliminates environmental concerns of toxic threats. Herein, we proposed a new strategy for the utilization of petrochemical-derived carbon black waste, a waste vanadium-bearing resource (V > 30000 ppm (10 ⁻⁶)). Chemical leaching was employed to extract metallic vanadium from the waste and the leachate containing V was used as an alternative raw material for the fabrication of vanadate nanomaterials. Through the screening of various metal cations, it was found that the contaminated Na⁺ during the leaching process showed strong competitive coordination with the vanadium ions. However, by adding foreign Ce³⁺ and Y³⁺ cations, two rare-earth vanadates, viz., flower-like CeVO₄ and spherical YVO₄ nanomaterials, were successfully synthesized. Characterization techniques such as scanning electron microscopy, transmission electron microscopy, X-ray diffraction, energy-dispersive X-ray spectroscopy, Fourier-transform infrared, and N₂ physisorption were applied to analyze the physicochemical properties of the waste-derived nanomaterials. Importantly, we found that rare-earth vanadate catalysts exhibited good activities toward the semi-hydrogenation of α,β-unsaturated aldehydes. The conversion of cinnamaldehyde and cinnamic alcohol selectivity were even higher than those of the common CeVO₄ prepared using pure chemicals (67.2% vs. 27.7% and 88.4% vs. 53.5%). Our work provides a valuable new reference for preparing vanadate catalysts by the use of abundant vanadium-bearing waste resources.