Donor-acceptor (D-A) type molecules with a skeleton consisting of a dimethylaminonaphthalene donor and an oxazaborine acceptor were designed as efficient electrochemiluminescence (ECL) luminophores with tunable intramolecular charge transfer (ICT). The D-A ECL luminophores demonstrated that the ICT characteristics play a critical role in the electrochemistry and ECL of luminophores in the presence of tri-n-propylamine, which was rationalised experimentally and computationally. Furthemore, dual-peaked ECL-potential behaviours of the luminophores were rationalised using two competitive pathway ECL mechanisms, elucidated through the use of spooling ECL spectroscopy.