4-cyano-4'-pentylbiphenyl (5CB) microdroplets coated with PAA-b-LCP were successfully made via microfluidics. Their functionalized interfaces were examined for lysozyme and bovine serum albumin detection, which could be easily visualized with an optical microscope under crossed polarizers by the radial-to-bipolar configurational change of the 5CB. This transition was strongly dependent on the electrostatic states of the proteins and PAA chains, which were controlled by the pH of the water. This study demonstrated a simple approach for the development of a liquid crystal-based sensor for label-free detection of proteins, which may have diverse applications in various biomedical fields.