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Surface modification and wetting state transformation of ZnO based nanomaterials have been extensively investigated due to their substantial roles in current industrial applications. In this work, we demonstrated the formation of highly crystalline and ordered Bi/ZnO nanorods arrays (Bi/ZNRs) grown on FTO substrate via a feasible hydrothermal method, as a function of reaction time (t). The lateral diameter of the nanostructures were found increased from 23 nm to 43 nm when the reaction time increased from 30 min to 90 min. An in-depth analysis and incisive mechanism of crystal growth under the function of reaction time were proposed. The crystal defect which originated from different Bi incorporation pathways has been declared as the main factor altering the optical energy, electrical properties and band structure of Bi/ZNRs. The Bi/ZNRs showed a higher localize current of 14.5 pA as compared to pristine ZNRs under an 6V applied bias condition, revealing the nature of Bi as a pentavalent dopant that contributed to a density of free electron. Additionally, the Bi/ZNRs also revealed a red shifted in optical energy band gap and exhibit a wetting transition from hydrophobic to hydrophilic textured surface. The novel nanostructures reported herein exhibit interesting physical and optical properties for the fabrication of high performance optoelectronic devices.