Mono- and di-anchoring gamma-pyranylidene-based organic dyes featuring D-pi-A and D-(pi-A)(2) architectures have been engineered as sensitizers for applications in Dye-Sensitized Solar Cells (DSSCs). Their photophysical, electrochemical and photovoltaic properties were further investigated. TD-DFT calculations were performed to rationalize the trends observed in the optical and electrochemical properties of the dyes. The investigation of the photovoltaic performances of this series of new dyes provided structure-property relationships where their Power Conversion Efficiencies (PCE) could be correlated to structural features, such as the length of the pi-conjugated spacer, the nature of the substituents on the pyranylidene electron donor moiety and the number of anchoring groups. Dye-Sensitized Solar Cells based on mono-anchoring dyes were more efficient than the corresponding cells based on di-anchoring analogues due to high dye loading. The highest Power Conversion Efficiency of 5.23% was achieved with the mono-anchoring 17a dye containing t-butyl substituent groups on the pyranylidene fragment and with one thienyl pi-conjugated spacer.