Fabrication and precise control of the physicochemical properties of multifunctional organic-inorganic hybrid nanocomposites find great importance in various research fields. Herein, we report the fabrication of a new class of luminescent hybrid coacervate droplets from CdTe quantum dots (QDs) and a poly(diallyldimethylammonium chloride) (PDADMAC) aqueous mixture. The colloidal stability of these droplets has been explored over wide ranges of composition, pH, and ionic strength. Although these hybrid droplets are quite stable in a low-ionic-strength medium (<100 mM NaCl) and neutral/basic pH (pH >6.5), they are unstable in a higher-ionic-strength medium (>100 mM NaCl) and acidic pH (pH <5.5). Our findings indicate specific electrostatic interactions between negatively charged QDs and positively charged PDADMAC behind the observed coacervation. They exhibit the preferential sequestration of organic dyes and serum albumins. The intrinsic luminescent properties of these hybrid droplets have been explored using confocal laser scanning microscopy (CLSM) and epifluorescence microscopy. CLSM reveals the formation of intrinsically luminescent hybrid droplets. In addition, mixed two-color luminescent droplets have been fabricated by simultaneously mixing green- and red-emitting QDs with PDADMAC aqueous solution. Epifluorescence imaging reveals highly photostable and nonbleaching photoluminescence (PL) from individual droplets as a consequence of efficient surface passivation by polymeric chains of PDADMAC. Moreover, using two-photon (2P) confocal imaging we have shown that these hybrid droplets are ideal candidates for 2P confocal imaging applications. The present study can be easily extended to fabricate a wide range of hybrid droplets with various inorganic counterparts having unique optoelectronic properties, which will further expand their applicability in nanocatalysis, bioimaging, and biosensing.