Water-in-oil droplets have emerged as promising microreactors for high-throughput biochemical analysis due to their features of reduced sample consumption and automated operation. For a typical screening application, droplets are often trapped for continuous monitoring of the reaction over an extended period, followed by the selective retrieval of targeted droplets based on the after-effect of biochemical reactions. While techniques for droplet trapping are well developed, retrieval of targeted droplets mainly demands complicated device fabrication or sophisticated control. Herein, facile and rapid selective droplet release is achieved by utilizing a new class of photoresponsive fluorosurfactant based on plasmonic nanoparticles. The intense photothermal response provided by this novel photoresponsive fluorosurfactant is capable of vaporizing the fluorocarbon oil at the droplet interface under laser illumination, resulting in a bubble releasing a trapped droplet on demand. A fully automated fluorescence-activated droplet release platform has also been developed to demonstrate its potential for droplet-based large-scale screening applications.