Our straightforward and scalable synthetic methodology enabled the efficient production of a diverse array of π-expanded derivatives. Systematic investigation of their optoelectronic properties revealed intense colors and fluorescence throughout the visible range. The observed spectral trends closely aligned with our design principles and were corroborated by electrochemical measurements and theoretical calculations, including time-dependent density functional theory (TD-DFT) and ring current analyses. Reactivity studies highlighted the indole-like behavior of indoloindolizines, demonstrating high regioselectivity in electrophilic substitutions and opening avenues for further functionalization.