Organic molecules and related nanomaterials have attracted extensive attention in the realm of electrochemiluminescence (ECL). Herein, a well-known electroluminescence (EL) dopant 2,3,6,7-tetrahydro-1,1,7,7,-tetramethyl-1H,5H,11H-10-(2-benzothiazolyl)quinolizino-[9,9a,1gh] coumarin (C545T) is selected as a new ECL illuminant, which shows a high photoluminescence quantum yield of nearly 100% and excellent ECL performance in the organic phase. For utilizing C545T to achieve ECL detection in aqueous solution, organic microrods of C545T (C545T MRs) were synthesized by a precipitation method. Cyclic voltammetry and differential pulse voltammetry of C545T and C545T MRs in acetonitrile or phosphate buffer showed one reduction and multiple oxidation peaks, suggesting that the multiple charge states of C545T could be produced by continuous electron- or hole-injection processes. The annihilated ECL emission of C545T and C545T MRs was observed using ECL transient technology. In the presence of triethanolamine (TEOA) or potassium persulfate (K2S2O8), C545T MRs can also give bright anodic and cathodic ECL emission at the GCE/water interface. The proposed ECL system not only has multichannel ECL emission but also shows intense yellow emission (569 nm) with a relative ECL efficiency of 0.81 when TEOA was used as a coreactant. Benefiting from the strong ECL emission of the C545T MRs/TEOA system and the quenching effect of dopamine (DA) on ECL, a convenient sensor for DA was developed with high selectivity and sensitivity.