We report experimental and computational studies of the spectroscopy and photochemistry of the CF2I radical, which was generated using pulsed discharge or photolytic techniques and trapped in Ar or Ne matrices held at similar to 5 K. Ground state calculations were performed using UM062X and UB3LYP density functionals and the UMP2, UCCSD, and CASPT2 ab initio methods, all with high-quality basis sets. The photochemical reaction path from the lowest-lying electronically excited state was mapped using the CASPT2//CASSCF methodology. A conical intersection was found to drive the excited state species to the photoproduct/reactant wells on the ground state potential energy surface. (C) 2010 Elsevier B.V. All rights reserved.