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In the present investigation, ZnO films co-doped with Mn and La were synthesized by the sol–gel technique. XRD analysis revealed that ZnO had a hexagonal structure. Mixed hexagonal and cubic phases appeared in ZnO containing Mn (1%) and La (1.5%). The grain size, d-spacing, unit cell, lattice parameters, atomic packing fraction, volume, strain, crystallinity, and bond length of co-doped ZnO films were determined as a function of doped ion contents. Through UV analysis, it was found that pristine ZnO had E_g = 3.5 eV, and it decreased when increasing the doping concentration, reaching the minimum value for the sample with 1% Mn and 1% La. The optical parameters of the films, such as absorption, transmittance, dielectric constants, and refractive index, were also analyzed. DSSCs were fabricated using the prepared ZnO films. For pure ZnO film, the values were: efficiency = 0.69%, current density = 2.5 mAcm⁻², and open-circuit voltage = 0.56 V. When ZnO was co-doped with Mn and La, the efficiency increased significantly. DSSCs with a ZnO photoanode co-doped with 1% Mn and 1% La exhibited maximum values of J_sc = 4.28 mAcm⁻², V_oc = 0.6 V, and efficiency = 1.89%, which is 174% better than pristine ZnO-based DSSCs. This material is good for the electrode of perovskite solar cells.