Highly efficient blue-emitting CdSe-derived core/shell gradient alloy quantum dots (CSGA QDs) with photoluminescence quantum yield (PL QY) of ca. 90% have been synthesized through a facile "one-pot" approach. CdSe nuclei are initially formed as core and gradient alloy shells such as CdSeS/ZnSeS simultaneously encapsulate the preformed CdSe core in an energy-gradient fashion eventually followed by coating with ZnS shells due to the faster precursor reaction kinetics of Cd and Se compared to analog of Zn and S. During the formation of core/shell structure, red-shifting of absorption/emission peaks followed by blue-shifting of analogues were observed due to the intradiffusion of sulfur anion to CdSe luminescent center. In this gradient architecture, interfacial lattice strain can be effectively alleviated, and thus high PL QY (ca. 90%) and enhanced photochemical stability can be achieved. The synthesized blue-emitting gradient alloy QDs with superior optical properties tunable in the range of 450-490 nm can be used for highly efficient blue-emitters and potentially applicable for the fabrication of white-light LEDs.