Complex liquid colloids hold great promise as transducers in sensing applications as a result of their tunable morphology and intrinsic optical properties. The multi-phase emulsion droplets show enhanced directional light emission due to total internal reflection in their high-index phase. The light emission characteristics of these multi-compartment droplets are strongly dependent on the droplets’ interfacial curvatures and refractive index contrast. Herein, we have designed and synthesized polymers in the interface between hydrocarbon and fluorocarbon phases to amplify the fluorescence difference. Fluorescent complex colloids represent a new approach for biosensing in liquid environments.