High extinction coefficients and easily tunable spectral properties of π - conjugated donor-acceptor dyes are of superior advantage for the design of new metal- free organic sensitizers for applications in dye-sensitized solar cells. Ultrafast transient absorption spectroscopy on the femtosecond and nanosecond time scales provided deep insights into the dependence of charge carrier dynamics in fully organic dye/TiO2 systems on i) the donor-acceptor distance, ii) the π-conjugation length, and iii) the coupling to TiO2 by different anchoring groups. Importantly, the observed differences in charge transfer dynamics justify the variations of photovoltaic performances of the dyes as applied in solar cell devices. This leads to the conclusion that the photoconversion efficiencies strongly depend on a delicate interplay between the dyes’ building blocks, i.e. the donor, the π-conjugated spacer and the anchor/acceptor moieties, and may easily be tuned by molecular design.