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Perovskite solar cells (PSCs) still suffer from varying degrees of optical and electrical losses. To enhance the light decoupling and capture ability of Planar PSCs, an ultra-thin PSC structure with an Al₂O₃ pyramid anti-reflection layer (Al₂O₃ PARL) is proposed. The effect of the structure of the Al₂O₃ PARL on the photoelectric performance of PSCs was investigated by changing various parameters. Under the AM1.5 solar spectrum (300–800 nm), the average light absorption rates and quantum efficiency (QE) of PSCs containing pyramid-array textured rear layers (PARLs) were significantly higher than those of planar PSCs. The Al₂O₃ PARL-based PSCs achieved a light absorption rate of 96.05%. Additionally, electrical simulations were performed using the finite element method (FEM) to calculate the short-circuit current density (J_SC), open-circuit voltage (V_OC), and maximum power (Pmax). Based on the maximum value of the average light absorbance, the geometric structure of the Al₂O₃ pyramid PSCs was optimized, and the optimization results coincided with the J_SC and QE results. The results of the electrical simulation indicated that the maximum J_SC was 23.54 mA/cm². Additionally, the J_SC of the Al₂O₃ pyramid PSCs was 22.73% higher than that of planar PSCs, resulting in a photoelectric conversion efficiency (PCE) of 24.34%. As a result, the photoelectric conversion rate of the solar cells increased from 14.01% to 17.19%. These findings suggest that the presence of the Al₂O₃ PARL enhanced photon absorption, leading to an increase in electron–hole pairs and ultimately improving the photocurrent of the solar cells.