After the first report in 2008, diketopyrrolopyrrole (DPP)-based small-molecule photovoltaic materials have been intensively explored. The power conversion efficiencies (PCEs) for the DPP-based small-molecule donors have been improved up to 8%. Furthermore, through judicious structure modification, DPP-based small molecules can also be converted into electron-acceptor materials, and, recently, some exciting progress has been achieved. The development of DPP-based photovoltaic small molecules is summarized here, and the photovoltaic performance is discussed in relation to structural modifications, such as the variations of donor-acceptor building blocks, alkyl substitutions, and the type of conjugated bridges, as well as end-capped groups. It is expected that the discussion will provide a guideline in the exploration of novel and promising DPP-containing photovoltaic small molecules.