Three types of fluorinated carbon, all in their original form and upon sequential chemical lithiations via n-butyllithium, were investigated by C-13 and F-19 solid-state NMR methods. The three starting CFx materials [where x=1 (nominally)] were fiber based, graphite based, and petroleum coke based. The aim of the current study was to identify, at the atomic/molecular structural level, factors that might account for differences in electrochemical performance among the different kinds of CFx. Differences were noted in the covalent F character among the starting compounds and in the details of LiF production among the lithiated samples.