Electrogenerated chemiluminescence (ECL) of CdSe hollow spherical assemblies (HSAs) was studied in aqueous system by entrapping them in carbon paste. In air-saturated strong alkaline solution three ECL processes were obtained at -1.2, +1.34 and +1.75 V versus Ag/AgCl without adding any special coreactants. The different ECL processes resulted from the electron transfer reactions between positively or negatively charged CdSe HSAs and some electrogenerated species. Selective quench of the anodic and cathodic ECL processes were achieved by controlling the solution pH value or the concentration of dissolved oxygen. Comparing the ECL processes of the entrapped CdSc nanocrystals with the entrapped HSAs, the architecture of the HSAs showed important effects on their ECL behaviors. The ECL features of HSAs entrapped in carbon paste depended on the applied potentials. CdSe HSAs could be developed as a new ECL system in aqueous system with some super points. (c) 2005 Elsevier B.V. All rights reserved.