The potency of heteroatom-doping in reshaping optoelectronic properties arises from the distinct electronegativity variations between heteroatoms and carbon atoms. By incorporating two heteroatoms with differing electronegativities (e.g., B = N), not only is the architectural coherence of π-conjugated systems retained, but also dipolar traits are introduced, accompanied by unique intermolecular interactions absent in their all-carbon analogs. Another burgeoning doping strategy, featuring the heteroatom-boron-heteroatom motif (X-B-X, where X = N, O), has captured growing attention. This configuration's coexistence of the boron-heteroatom unit and an isolated heteroatom stimulates mutual modulation in the dipole of the boron-heteroatom unit and the heteroatom's electronegativity. In this Feature article, we present an encompassing survey of XBX-doped π-conjugated systems, elucidating how the integration of the X-B-X unit induces transformative structural and property changes within π-conjugated systems.