ABSTRACT Plastic recycling, especially polyvinyl chloride (PVC), represents an emerging research frontier yet remains a great challenge. In this work, we have realized the upgradation of PVC to olefins and other chlorinated chemicals with polypropylene (PP)‐derived carbon nanotubes. In particular, PP was mixed with Ni 2 O 3 powder and converted into CNTs‐capped Ni nanoparticles (Ni/CNTs) under high temperature, which was used as the catalyst to trigger the dechlorination of PVC and the chlorination of tetrahydrofuran (THF) with light irradiation. Note that the dechlorination efficiency reaches 96.3% at a THF conversion of 97.9%, with a 4‐chloro‐1‐butanol selectivity of 93.3% under the optimal conditions. Impressively, the dechlorinated PVC (DPVC) can be further converted into C 1 −C 4 alkanes and C 2 −C4 olefins with a total selectivity of 49.1% and 50.9%, respectively, over Ni/CNTs. This work provides a feasible strategy for upcycling PVC and PP, which demonstrates great potential for environmentally friendly waste plastic management.