AbstractThe relationship between emission and ligand restriction of a series of ZnSe/ZnS quantum dots (QDs) encapsulated in nanoparticles is investigated systematically via experiments and quantum theory. The QDs have a ZnSe core and a ZnS shell, capped with hydrophobic ligands (triotylphosphine oxide/hexadecylamine), allowing them to be entrapped in a model biomembrane, bicelle, made of zwitterionic dipalmitoyl and dihexanoyl phosphatidylcholines and charged dipalmitoyl phosphatidylglycerol. Enhanced photoluminescence is observed upon encapsulation, depending on the QD‐to‐lipid ratio. Transmission electron microscopy and small‐angle X‐ray scattering confirm that QDs are preferably situated at the rim of bicellar discs. A simplified quantum dissipation heat‐bath theory is proposed to correlate the enhancement with slower nonradiative processes caused by the restriction‐in‐motion (RIM) of the surface ligands. However, Förster resonance energy transfer due to QD aggregation counteracts the effect.