In this study, a novel composite carbon nanotube material, designated as PCN/ZIF-CNT, was synthesized for the first time from a PCN-600(Ni)@ZIF-67(Co, Cu) precursor. The metal-organic framework (MOF) ZIF-67 was initially grown on a nickel-porphyrinic MOF, PCN-600(Ni), which contains iron oxide nodes. This hierarchical structure was subsequently subjected to controlled pyrolysis under a mixed acetylene/hydrogen atmosphere at 800 °C, yielding a composite structure of carbon nanotubes embedded with multimetallic nanoparticles (Co, Ni, Fe, Cu). The successful formation was confirmed by various techniques, including XRD, SEM, TEM, and elemental analysis. Photoluminescence (PL) studies revealed a significant decrease in the emission intensity of the final composite compared to its precursor, providing strong evidence for efficient charge transfer and effective suppression of charge carrier (electron-hole) recombination within the architecture. This material was then employed as a photocatalyst for the selective oxidation of benzyl alcohol to benzaldehyde under visible-LED-light irradiation. Under optimized conditions, benzaldehyde was obtained with a yield of approximately 99% and high selectivity. The photocatalytic performance remained stable over four consecutive reaction cycles, demonstrating robustness. This exceptional performance is attributed to the unique composite structure, where the carbon nanotubes provide pathways for rapid charge transport, and the encapsulated multimetallic nanoparticles serve as highly active catalytic sites.