Perfluoropolyethers are a well known and widely used family of polymers, suitable as protectives. Their main drawback is the lack of solubility, which is complete only in chlorofluorocarbons. In this work a series of A‐B‐A block copolymers (FluoPLA), with a relative low molecular weight, were prepared by ROP of L‐ and D,L‐lactide (PLA) in the presence of a hydroxy‐terminated perfluoropolyether as macroinitiator. In fact the use of block copolymers leads to different advantages, i.e. a limited segregation phenomena and higher polymer solubility. The resulting polymers were characterized (by NMR, IR, HPLC‐SEC, DSC, LS) and tested as potential protective and surface modifiers for cultural heritage (ESEM‐EDS, solar‐box technique, colorimeter analysis).