The stabilization of fluorous oil droplets in aqueous environment is a critical issue in the preparation of emulsified systems for biomedical applications and in emulsion polymerization technology, due to the extreme immiscibility of aqueous and fluorous phases. We present here a detailed study on the behavior of the hydrophobin HFBI, i.e. a small natural protein endowed with exceptional surface activity, at the interface between aqueous and fluorous phases. HFBI behaves as an efficient and sustainable surfactant at remarkably low concentrations and forms a strong and elastic film at the interface between the two phases. We also show proof-of-concept experiments on the use of HFBI as a surfactant in fluorous oil/water emulsified systems and in microfluidic circuits.