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In this contribution, a unique donor‐acceptor conjugated organic‐small‐molecule photothermal material, namely GDPA‐QCN, is presented. Bulky dendritic triphenylamine (GDPA) was grafted onto quinoxaline‐6,7‐dicarbonitrile (QCN) with a phenyl ring as a bridge to form an "umbrella" architecture. Benefited from the particular molecular structure, in solid state, GDPA‐QCN molecules adopted a loose packing mode due to the steric effect of "umbrella head" dendritic triphenylamine and flexible molecular structure feature, which allows efficient intramolecular motions and consequently elevates energy dissipation by taking the pathway of thermal deactivation within broad absorption range. The GDPA‐QCN solid has high solar‐thermal conversion efficiency with an absorption range from 300 to 1100 nm, which can promote superior water purification and electricity generation performance. [ABSTRACT FROM AUTHOR]