Simple lanthanide cyclopentadienyl (Cp) complexes can photochemically cleave the sp³ carbon-chlorine bond of unactivated chlorinated hydrocarbons including polyvinyl chloride (PVC). The excited state lifetimes of these simple complexes are among the longest observed for cerium complexes (175 ns for [(Cp^Me4)₂Ce(μ-Cl)]₂) and the light absorption by the Cp ligand is efficient, so photocatalytic reactivity is enhanced for cerium and now also made possible for neighboring, normally photoinactive, lanthanide congeners.