New dithiafulvenyl-pi-phenothiazine dyes have been devised and prepared for dye-sensitized solar cells. Various pi-spacers have been successfully introduced into the skeleton of dithiafulvenyl and phenothiazine unit to generate novel D-pi-D-A dyes (DPP-1 similar to 4). All dyes have been characterized with NMR, HRMS, UV-vis and fluorescence spectra, and taken into cyclic voltammetry measurements. The devices of new dyes have been determined by photoelectrochemical experiments (IV, IPCE and EIS), in which, solar cell of DPP-4 with biphenyl ring pi-spacer enhances obviously its photoelectric conversion efficiency to 7.66% reaching 94% of N719-based standard cell and displays good long-term stability with quasi-solid-state electrolyte. Density functional theory (DFT) calculations of new dyes provide further insight into the molecular geometries and the impacts of the torsion angles on their photovoltaic performance. Large dihedral angles in DPP dyes induce good charge separation for efficient unidirectional flow of electron from donor to acceptor. (C) 2016 Elsevier B.V. All rights reserved.