Dye-sensitized solar cells (DSSCs) have become a validated and economically credible competitor to the traditional solid-state junction photovoltaic devices. DSSCs based on biopolymer gel electrolyte systems offer the perspective of competitive conversion efficiencies with a very low-cost fabrication. In this paper, a new starch-based biopolymer gel electrolyte system is prepared by mixing lithium iodide and iodine with bare and citric acid cross-linked potato starches with glycerol as the plasticizing agent. The effect of the preparation methods on the starch cross-linking degree as well as the photoconversion efficiency of the resulting DSSC cells is carefully analyzed. Fourier transform spectroscopy, X-ray diffraction, and scanning electron microscopy were used to characterize the morphology and conformational changes of starch in the electrolytes. The conductivity of the biopolymer electrolytes was determined by electrochemical impedance spectroscopy. DSSC based on the starch-gel polymer electrolytes were characterized by photovoltaic measurements and electrochemical impedance spectroscopy. Results clearly show that the cross-linking increases the recombination resistance and open circuit voltage (V OC ) of the DSSC, and thereby the photoconversion efficiency of the cell. In particular, electrolytes containing 1.4 g bare and cross-linked starches showed ionic conductivities of σ = 1.61, 0.59, 0.38, and 0.35 S cm −1 , and the corresponding DSSCs showed efficiencies of 1.2, 1.4, 0.93, and 1.11%, respectively.