After a broad scouting based on quantum chemical calculations, optical absorption measurements in the vacuum ultraviolet (VUV) wavelength region between 140 and 190 nm were performed on a narrower series of commercial and experimental liquids. By elimination of sources of external contamination, mainly due to atmospheric gases, the analysis of the contributions to the absorption related to the backbone structure and to the chain end composition allowed the synthesis of a novel family of linear perfluoropolyethers (PFPEs) with optical absorbance at 157 nm between 0.3 and 0.6 cm(-1) in a broad range of compositions and molecular weights. The dependence of the optical threshold on the PFPE composition demonstrates that -OCF2- is the most transparent segmental unit in the VUV region.