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Photo-annealing treatment titanium chelate (TIPD) layer, which was the indium tin oxide (ITO) interface-modified layer, was used as a replacement for the thermal annealing treatment of TIPD. The power conversion efficiency (PCE) of photo-annealed TIPD-based polymer solar cells (PSCs) is quite low in the initial stage, but it dramatically increases following constant light illumination, and the cell achieves a saturated state after 9 min of light illumination. By employing the mixed films poly[1-(5-(4,8-bis(5-(2-ethylhexyl)-4-fluorothiophen-2-yl)-6-methylbenzo[1,2-b:4,5-b′]dithiophen-2-yl)thiophen-2-yl)-5,7-bis(2-ethylhexyl)-3-(5-methylthiophen-2-yl)-4H,8H-benzo[1,2-c:4,5-c′]dithiophene-4,8-dione] (PBDB-TF) and 2,2′-((2 Z ,2′ Z)-(((4,4,9,9-tetrakis-(4-hexylphenyl)-4,9-dihydro-sindaceno[1,2- b :5,6- b ']-dithiophene-2,7-diyl)bis(4-((2-ethylhexyl)oxy)thiophene-5,2-diyl))bis(methanylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene)) dimalononitrile (IEICO-4F) as photoactive layers, we improved the photovoltaic performance. The enhanced photovoltaic performance of TIPD films treated with photo-annealing was explained by the increased short-circuit current density (J SC). Efficient medium- and long-wavelength light transmittance and suppression of charge recombination are beneficial for enhancing the J SC value. • Titanium chelate (TIPD) films by photo annealing treatment is efficient electron extraction layer (EEL) material. • The photo annealing treatment TIPD films achieve efficient charge transport and weak charge recombination. • The efficient medium and long wavelength light transmittance efficiency for photo annealing TIPD films. [ABSTRACT FROM AUTHOR]