A non-vacuum processing method for preparing polymer-based ZrO2/TiO2 multilayer structure antireflection coating (ARC) films for crystalline silicon solar cells by spin coating is introduced. Initially, ZrO2, TiO2 and surface deactivated-TiO2 (SD-TiO2) based films were examined separately and the effect of photocatalytic properties of TiO2 film on the reflectivity on silicon surface was investigated. Degradation of the reflectance performance with increasing reflectivity of up to 2% in the ultraviolet region was confirmed. No significant change of the reflectance was observed when utilizing SD-TiO2 and ZrO2 films. Average reflectance (between 300 nm-1100 nm) of the silicon surface coated with optimized polymer-based ZrO2 single or ZrV/SD-TiO2 multilayer composite films was decreased down to 6.5% and 5.5%, respectively. Improvement of photocurrent density (Jsc) and conversion efficiency (eta) of fabricated silicon solar cells owing to the ZrO2/SD-TiO2 multilayer ARC could be confirmed. The photovoltaic properties of Jsc, the open-circuit photo voltage (V-OC), the fill factor (FF), and the eta were 31.42 mA cm(-2), 575 mV, 71.5% and 12.91%. Efficiency of the solar cells was improved by the ZrO2-polymer/SD-TiO2 polymer ARC composite layer by a factor of 0.8% with an increase of Jsc (2.07 mA cm(-2)) compared to those of fabricated without the ARC.