The motivation of this work is to create luminescent rare earth/polymer films with outstanding water-resistance and superhydrophobicity. Specifically, the emulsion polymerization of styrene leads to core particles. Then core-shell-structured polymer nanoparticles are synthesized by copolymerization of styrene and acrylic acid on the core surface. The coordination reaction between carboxylic groups and rare earth ions (Eu(3+) and Tb(3+)) generates uniform spherical rare earth/polymer nanoparticles, which are subsequently complexed with PTFE microparticles to obtain micro-/nano-scaled PTFE/rare earth films with hierarchical rough morphology. The films exhibit large water contact angle up to 161° and sliding angle of about 6°, and can emit strong red and green fluorescence under UV excitation. More surprisingly, it is found that the films maintain high fluorescence intensity after submersed in water and even in aqueous salt solution for two days because of the excellent water repellent ability of surfaces.