The development of new materials for solar‐to‐energy conversion should consider stability, ease of fabrication, and beneficial photophysical properties. In this context, a set of novel π‐conjugated building blocks, with phospha‐ and arsaalkenes possessing a unique dithienyl annulated heterofulvenoid core, have been prepared as air‐ and moisture‐stable sensitizers. These compounds unify electron‐donor and ‐acceptor moieties, making them potential candidates for light‐harvesting applications. Optical characterization of these systems was performed by steady‐state and time‐resolved absorption spectroscopy, supported by time‐dependent DFT calculations. Tuning of the optical properties of these systems can be achieved by varying the pnictogen element at the bridgehead position, giving a bathochromic shift of ≈40 nm and coordinating the phosphaalkene towards gold AuI centers. The latter results in a ≈2000‐fold extension of the ≈10 ps lifetime of uncoordinated systems well into the ns regime.