Stimuli-responsive surface adhesion regulation is widely used in automated assembly systems, intelligent pick-up and placement systems, and soft crawling robots. However, in the actual separation process, it tends to produce separation residue or excessive adhesion. Therefore, how to regulate surface adhesion on demand is a significant challenge. Herein, inspired by the anisotropic adhesion behavior of butterflies and the controlled adhesion behavior of octopuses, based on molecular conformational rearrangement and anisotropic structures, a humidity-responsive PES-PI/PDMS composite surface is achieved to meet the needs of controllable adhesion orientation and strength, which could be used for an intelligent transfer system (grasping and releasing and anisotropic transporting). Humidity can effectively tune the hydrogen bonding and the interaction between polymers, resulting in excellent self-healing and durability properties of the composite surface. Moreover, humidity could adjust the surface transmittance as well, making it possible to be used in humidity sensing and in a detection and encryption/decryption system to enhance environmental monitoring and information protection capabilities. This work not only establishes a method for the fabrication of innovative "high-flexibility" adhesive materials but also provides approaches for the design and development of intelligent response devices.