The invention discloses lead-free glass powder, lead-free glass powder slurry, a large-area dye-sensitized solar cell as well as a preparation method and application thereof. The lead-free glass powder comprises the following components: 10-20% of SiO2, 5-15% of B2O3, 40-70% of Bi2O3, 1-10% of ZnO, 1-10% of Al2O3, 0.5-5% of Na2O, 1-5% of BaO and 2-7% of CaO. The lead-free glass powder slurry comprises the following components: 70-80% of the lead-free glass powder, 15-25% of an organic carrier and 1-5% of additives. According to the formed dense glass corrosion-resistant protective layer, the corrosion resistance of a conductive silver grid can be improved; and moreover, due to the glass powder around the FTO conductive glass, a photo-anode and a counter electrode are sealed, and by virtue of a whole face printing manner, the quantity of holes is reduced, the packaging technology is simplified, leakage of electrolyte can be slowed down, and the service life of the cell is prolonged.