In conclusion, through the cooperative interactions between an engineered nonheme Fe enzyme and a judiciously selected photocatalyst, we developed dual photometallobiocatalytic decarboxylative radical azidation, thiocyanation and isocyanation of redox-active N-hydroxyphthalimide esters. Mechanistically, a radical rebound step involving nonheme enzymatic Fe(III)-N3, Fe(III)-NCS and Fe(III)-NCO intermediates represented the unifying mechanism underlying these transformations. The evaluation of an in-house collection of nonheme Fe enzymes allowed the identification of several promising starting points for the development of photometallobiocatalytic radical transformations. In particular, metapyrocatechase (MPC), a nonheme Fe extradiol dioxygenase which has not been studied in prior new-to-nature biocatalysis research, was identified as an excellent biocatalyst. Enabled by high-throughput photobiocatalysis, further directed evolution led to MPC triple variants with substantially improved activity and enantioselectivity for azidation, thiocyanation and isocyanation. These evolved MPC variants allowed an array of primary, secondary and tertiary radical precursors to be transformed, leading to useful products with excellent enantioselectivity. Further chemical derivatization of these C-N and C-S bond forming products demonstrated the synthetic utility of these chiral building blocks. Computational studies afforded further insights into the mechanism and origin of enantioselectivity in the present nonheme photobiocatalysis. An enantioinduction model was proposed based on MD simulations of the alkyl radical approaching the Fe(III)-N3 in the enzyme active site, where the F302Y and L155F mutations introduced in directed evolution play important roles in affecting the preferred binding poses and the orientation of the prochiral radical intermediate prior to the enantiodetermining radical rebound. Overall, engineered nonheme Fe enzyme MPC and related extradiol dioxygenase may find broader applications in other non-native biocatalytic reaction. We expect the use of cooperative photobiocatalysis to inspire the further development of a wider range of synthetically useful transformations catalyzed by nonheme Fe enzymes.