We report the synthesis, electrochemistry, and electrogenerated chemiluminescence of a series of star-shaped donor-acceptor (D-A) molecules. The star-shaped molecules consist of an electron-deficient 1,3,5-triazine core with three fluorene arms substituted with diarylamino (TAM1-TAM3) or carbazolyl (TAM4) electron donors. Cyclic voltammetry of TAM1-TAM3 shows that the reduction consists of one wave of single electron transfer to the core, while the oxidation exhibits a single peak of three sequential electron-transfer processes, with the formation of a trication. The carbazole-containing molecule TAM4 after oxidation undergoes a subsequent rapid chemical reaction to produce a dimer (via the overall coupling of two radical cations with the loss of two protons). The dimer electrooxidizes more easily than the monomer of TAM4. With continuous cycling on the oxidation side, a conductive polymer film is formed on the surface of the working electrode. Because of the presence of the acceptor (triazine) center and strong donors in the arms (diarylamine or carbazole), TAM1-TAM3 exhibit large solvatochromic effects with emissions ranging from deep blue (428 nm) to orange-red (575 nm) depending on the solvent polarity. These star-shaped molecules show high PL quantum yields of 0.70-0.81. The electrogenerated chemiluminescence (ECL) of TAM1-TAM3 in nonaqueous solutions showed strong ECL that could be seen with the naked eye in a well-lit room. Because the enthalpy of annihilation is higher than the energy required for formation of the singlet excited state, the ECL emission is believed to be generated via S-route annihilation. However, TAM4 shows weak annihilation ECL because of the production of polymer film on the electrode surface during oxidation cycles. However, by limiting the potential region only to the reduction side and using benzoyl peroxide (BPO) as a coreactant, strong ECL of TAM4 can be obtained.