This project aims to develop a hydrodefluorination (HDF) method exploiting immobilized TiIII-H species on heterogeneous Ziegler-Natta (ZN) catalysts, employing high-throughput experimentation (HTE) and solid-state analysis techniques. Studies on the model substrate perfluoropyridine (PFPy) highlight the ability of ZN systems to engage in HDF. H2 gas is used as a promoter in the reaction to speed up the regeneration of the active species. Activity and selectivity can be influenced by the makeup of catalytic formulation. Turnover numbers (TONs) in the order of >10E4 can be inferred under the assumption that only 1% of the Ti particles on the catalyst are active. ZN systems are cheap, tunable and a wealth of information from 70 years of research can be exploited. Selective HDF of per- and polyfluorinated substrates could yield novel building blocks for e.g. the pharmaceutical industry