The high molar absorption coefficient organic D-π-A dye C220 exhibits more than 6% certified electric power conversion efficiency at AM 1.5G solar irradiation (100 mW cm-2) in a solid-state dye-sensitized solar cell using 2,2′,7,7′-tetrakis(N,N-dimethoxyphenylamine)-9,9′- spirobifluorene (spiro-MeOTAD) as the organic hole-transporting material. This contributes to a new record (6.08% by NREL) for this type of sensitized heterojunction photovoltaic device. Efficient charge generation is proved by incident photon-to-current conversion efficiency spectra. Transient photovoltage and photocurrent decay measurements showed that the enhanced performance achieved with C220 partially stems from the high charge collection efficiency over a wide potential range. © 2011 American Chemical Society.