Traditional organic luminescent materials typically rely on through-bond conjugation (TBC) within rigid structures to promote π-electron delocalization, thereby achieving high fluorescence quantum yields and tunable emission wavelengths. However, in recent years, anomalous visible-light emission has been observed in non-TBC systems lacking π-electrons, such as polyethylene glycol and polyethylenimine, overturning the conventional understanding of organic luminescence mechanisms. To address this scientific challenge, our team has designed and synthesized a new class of multiarylalkane systems, systematically exploring a novel luminescence mechanism driven by through-space conjugation (TSC). In this talk, the underlying mechanism and structure–property relationships of TSC will be elaborated, followed by demonstrations of how this principle enables the construction of new organic luminophores, including the development of the smallest known near-infrared organic emitter to date.