The synthesis of a 2-monobrominated dithieno[3,2-b:2′,3′-d]phosphole has opened the access to a series of highly luminescent π-conjugated oligomers that link two dithienophosphole units via a variety of aromatic spacers. The nature of the linking mode was found to have a significant impact on the photophysical properties of the system as a whole, either considerably improving the molar absorptivity of the new extended chromophores, or providing luminescent materials with red-shifted emission features and substantial photoluminescence quantum yields.