A novel synthetic method was developed for the controlled functionalization of fluorinated polyhedral oligomeric silsesquioxanes (F-POSS), which are useful as low surface energy materials for superhydrophobic and superoleophobic materials. Utilizing triflic acid, open-cage compounds were created and then reacted with a variety of dichlorosilanes to produce functional F-PUSS structures possessing alkyl-, aryl-, and acrylate-based moieties. The crystal structure for an endo,endo-disilanol F-POSS compound was determined by single-crystal X-ray diffraction. The chemical structures were confirmed using multinuclear NMR spectroscopy (H-1, C-13, F-19, and Si-29), FT-IR, and combustion analysis. Dynamic contact angle measurements of these compounds were taken with water and hexadecane. These novel structures were found to possess excellent wetting-resistant behavior, similar to that of the parent F-POSS compound. They are the first well-defined fluorinated nano-building blocks with a controlled level of reactive functionality for the development of new superhydrophobic and superoleophobic materials.