Polyaniline modified zinc oxide (PANI-ZnO) photocatalyst composites were synthesized by focusing on dissolution disadvantage of ZnO. In-Situ chemical oxidation polymerization method was performed under neutral conditions (PANI-ES) whereas in hybridization method physical blending was applied using emeraldine base of polyaniline (PANI-EB). PANI-ZnO composites were prepared in various ratios of aniline (ANI) to ZnO as 1%, 3%, 6% and 9%. The alterations on the structural and morphological properties of PANI-ZnO composites were compared by Fourier Transform Infrared (FT-IR), Raman Spectroscopy, X-ray Diffraction (XRD) and Scanning Electron Microscopy-Energy Dispersive X-ray Analysis Unit (SEM-EDAX) techniques. FT-IR and Raman spectroscopy confirmed the presence of PANI in all composites. SEM images revealed the morphological differences of PANI-ZnO composites based on PANI presence and preparation methods. Photocatalytic performances of PANI-ZnO specimens were investigated by following the degradation of methylene blue (MB) in aqueous medium under UVA irradiation. The effects of catalyst dose and initial dye concentration were also studied. MB degradation was followed by both decolorization extents and removal of aromatic fractions. PANI-ZnO composites expressed enhanced photocatalytic performance (~95% for both methods) as compared to sole ZnO (~87%). The hybridization method was found to be more efficient than the In-Situ chemical oxidation polymerization method emphasizing the significance of the neutral medium.