A perfluoropolyether thiol compound comprises a perfluoropolyether segment, at least one mercapto group (—SH), and at least one intervening divalent carbonylimino moiety (—C(═O)—NR—, wherein R is hydrogen or alkyl). The compound can be produced, for example, by a ring-opening reaction of thiolactones with perfluoropolyether-substituted, primary or secondary amines. The compound can be used, for example, as a polymerization chain transfer agent, as an intermediate for the preparation of functional group-containing fluorochemical derivatives such as disulfides, and as a fluorinated surface treatment.