The high performance and low cost of dye-sensitized solar cells (DSSCs) have drawn great interest from both academic and industrial circles. The research on exploring novel efficient sensitizers, especially on inexpensive metal-free pure organic dyes, has never been suspended. The donor–π bridge–acceptor (D–π–A) configuration is mainstream in the design of organic sensitizers due to its convenient modulation of the intramolecular charge-transfer nature. Recently, it has been found that incorporation of additional electron-withdrawing units (such as benzothiadiazole, benzotriazole, quinoxaline, phthalimide, diketopyrrolopyrrole, thienopyrazine, thiazole, triazine, cyanovinyl, cyano- and fluoro-substituted phenyl) into the π bridge as internal acceptors, termed the D–A–π–A configuration, displays several advantages such as tuning of the molecular energy levels, red-shift of the charge-transfer absorption band, and distinct improvement of photovoltaic performance and stability. We apply the D–A–π–A concept broadly to the organic sensitizers containing additional electron-withdrawing units between electron donors and acceptors. This review is projected to summarize the category of pure organic sensitizers on the basis of the D–A–π–A feature. By comparing the structure–property relationship of typical photovoltaic D–A–π–A dyes, the important guidelines in the design of such materials are highlighted.