The C-C bond in non-activated cyclopropanes can be intramolecularly cleaved with an electrochemically generated amidyl radical forming oxazolines. In the presence of TBABF4, this provides 1,3-oxyfluorination products. C-C bond cleavage of cyclopropane proceeds with inversion of the configuration, suggesting an intramolecular homolytic substitution (SHi) mechanism. The performance of TBABF4 as an efficient fluoride source was explained by accumulation of the BF4- anion at the anode surface, at which a carbocation is formed by the oxidation of the C-centered radical.