Soft robots adapt to complex environments for autonomous locomotion, manipulation, and perception are attractive for robot-environment interactions. Strategies to reconcile environment-triggered actuation and self-powered sensing responses to different stimuli remain challenging. By tuning the in situ vapor phase solvent exchange effect in continuous electrospinning, an asymmetric highly-aligned all-fiber membrane (HAFM) with a hierarchical “grape-like” nanosphere-assembled microfiber structure (specific surface area of 13.6 m2 g−1) and excellent mechanical toughness (tensile stress of 5.5 MPa, and fracture toughness of 798 KJ m−3) is developed, which shows efficient asymmetric actuation to both photothermal and humidity stimuli. The HAFM consists of a metal-organic framework (MOF)-enhanced moisture-responsive layer and an MXene-improved photothermal-responsive layer, which achieves substantial actuation with a bending curvature up to ≈7.23 cm−1 and a fast response of 0.60 cm−1 s−1. By tailoring the fiber alignment and bi-layer thickness ratio, different types of micromanipulators, automatic walking robots, and plant robots with programmable structures are demonstrated, which are realized for self-powered information perception of material type, object moisture, and temperature by integrating the autonomous triboelectric effect induced by photothermal-moisture actuation. This work presents fiber materials with programable hierarchical asymmetries and inspires a common strategy for self-powered organism-interface robots to interact with complex environments.