We present EPR analysis of the reaction of ethyl iododifluoroacetate with 1-tetradecene in the presence of Zn + NiCl2 x 6H2O, confirming the mechanistic studies that provide evidence of a single electron transfer process. We have trapped for the first time the ethoxycarbonyldifluoromethyl radical with a variety of spin traps, such as phenyl tert-butyl nitrone (PBN), 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), 2-methyl-2-nitrosopropane (MNP), and 2-nitro-2-nitrosopropane (NNP), and the EPR spectra of the corresponding adducts have been recorded. In a second step the ethoxycarbonyldifluoromethyl radical adds to the olefin to furnish a second radical intermediate, which can be trapped with NNP. Evidence of this second radical was obtained by EPR only with electron-rich olefins, such as alpha-methylstyrene and 2,4,6-trimethylstyrene, and the new adducts were recorded and interpreted. In addition, we also report the EPR spectra of the corresponding adducts when other alkylating reagents are used, such as ethyl iodoacetate, n-perfluorohexyl iodide, methyl omega-iodohexadecanoate, and n-butyl iodide.