For the quasi-solid-state electrolyte in dye-sensitized solar cells (DSSCs), the selection and optimization of components is a decisive process for high photovoltaic performance while maintaining stability. In this work, a two-phase polymer gel system based on PEO and PEGDME formed by chemical crosslinking is used as quasi-solid electrolyte in DSSCs. Through components of preparation solvent, iodine and GuSCN control, the photoelectric conversion efficiency of QS-DSSCs reaches 7.66%, especially the open-circuit voltage reaches 793 mV due to the self-assembly and ionic conductivity promotion. It lays a solid foundation for probing its potential value of quasi solid dye-sensitized solar cells.