In this study, we established a post-functionalization route to covalently incorporate anthracene moieties into poly(vinyl chloride) (PVC) while retaining PVC’s processability. Azide-functionalized PVC (PVC–N3) was prepared by nucleophilic substitution of C–Cl units, and an alkyne-terminated anthracene derivative was synthesized from anthracenemethanol via propargyl ether formation. The two components were coupled through Cu(I)-catalyzed azide–alkyne cycloaddition (CuAAC) to yield anthracene-functionalized PVC (PVCfAN). Formation of triazole linkages and anthracene incorporation were confirmed by FTIR and ¹H NMR, and the functionalization level was quantified from proton integration. This synthetic approach is expected to facilitate future development of processable anthracene-containing PVC materials.