The efficient synthesis and photophysical properties of a series of ambipolar donor-acceptor-donor systems is described where the acceptor is dibenzothiophene S,S-dioxide and the donor is fluorene, carbazole, or arylamine. The systems exhibit intramolecular charge transfer (ICT) states (of variable ICT character strengths) leading to fluorescence emission ranging from deep blue to green with moderate to high photoluminescence quantum yields. The emission properties can be effectively tuned by systematically changing the position of substitution on both donor and acceptor units (which affects the extent of conjugation) and the redox potentials of the donor units. The results are supported by cyclic voltammetric data and TD-DFT calculations.