Wearable and flexible chemical sensors are attracting attention for the healthcare and environmental applications due to their desirable operation safety, high flexible and enable to realize real-time detection. However, a major challenge in creating flexible chemical sensors is the insufficient activity and durability of the materials currently employed as sensing layers for gas molecule adsorption and reaction. Herein, we describe an ultra-sensitive flexible sensing platform that was based on efficient 1D/2D hetero-structure nanofiber consisting of a 1D TiO2 nanofiber wrapped in a shell of Bi2WO6 nanosheets. We also demonstrated the well-designed multi-channel sensitization effects in the electrosensitive, including the unique structural advantage, the grain boundary effect, and hetero-interface effect could synergistically improve electronic transform and gas molecules absorption at the interfaces. As a result, flexible sensor based on the 1D/2D hetero-structure nanofiber exhibit good mechanical stable and high selective sensitivity to ethanol gas molecules under room temperature. Thus, the introduction of hetero-interface and grain boundary provides a new avenue towards realizing highly sensitive and stable flexible sensing device.