When conjugate molecules are self-assembled on the surface of semiconductors, emergent properties resulting from the electronic coupling between the conjugate moieties are of importance in the interfacial electron-transfer dynamics for photoelectrochemical and optoelectronics devices. In this work, we investigate the self-assembly of triphenylamine-oligothiophene-peryle-nemonoimide (PMI) molecules, denoted as BH4, on metal oxide surfaces via UV-vis absorption, photoluminescence, and transient near-infrared absorption spectroscopies and molecular dynamics simulations, and we report the excimer formation due to the pi-pi interaction of the PMI units between the neighboring dye molecules. To our best knowledge, this is the first experimental observation of intermolecular excimer formation when conjugate donor-acceptor molecules form a self-assembled monolayer. In addition, a long-lived (4.3 mu s) intermolecular charge separation is observed, and a new excimer-mediated intermolecular charger-transfer mechanism is proposed. This work demonstrates that, through the design of dye molecules, the excited complexes or aggregates can provide a pathway to slow down the recombination rate in photoelectrodes that utilize donor-acceptor dyad molecules.