Ultrafast transient absorption spectroscopy, NOESY-NMR, and EPR spectroscopy shed light on how pi-pi stacking interactions combined with electrostatic interactions can be used to form stable ion-pair complexes between pyrylium and tetraarylborate ions in which the interaction of the pi-delocalized clouds promotes the observation of new radiative processes and also electron transfer processes excitation using visible light. The results exhibit a striking combination of properties, chemical stability and photophysical and photochemical events, that make these ion-pair complexes as a step toward the realization of chromophore/luminescent materials and also their use as a new monophotoinitiator system in radical polymerization reactions.