Photochromic materials have attracted considerable attention for their practical applications in optoelectronic devices. In this study, we developed the photochromic liquid core nanocapsules by polymerization of oil-in-water (O/W) nanoemulsion monomer droplets on the basis of Hansen solubility parameters. The thermoresponsive amphiphilic block copolymers (POEGMAm-b-PStn and POEGMAm-b-PMMAn) were synthesized by sequential reversible addition fragmentation chain transfer (RAFT) polymerization of hydrophilic oligo(ethylene glycol) methyl ether methacrylate and hydrophobic styrene or MMA. The O/W nanoemulsion methyl methacrylate (MMA) droplets, dissolving dipropylene glycol methyl-n-propyl ether (DPMNP) and (E)-3-(adamantan-2-ylidene)-4-[1-(2,5-dimethyl-3-furyl) ethylidene]dihydro-2,5furandione (Aberchrome 670) as a core liquid and a photochromic dye, respectively, were obtained through the phase inversion temperature emulsification technique using POEGMAm-b-PStn as a surfactant. As theoretically predicted in terms of the spreading coefficients, the DPMNP solution of Aberchrome 670 was successfully encapsulated by coacervation of the crosslinked PMMA condensed phase. Aberchrome 670 dissolved in a liquid core was found to photoisomerize twice as fast as that dispersed in the solid polymer matrices.