Hypothesis: Hierarchically structured surfaces including sensitive materials presents the advantage to exalt wettability variation due to the combination of micro structure effect directed by Cassie Baxter and/or Wenzel behaviour which is tuned by the surface energy variation of sensitive polymer films. Experiments: Herein is reported the synthesis and the hierarchical structuration of a pH sensitive diblock copolymer P(S-stat-MMA)-b-P4VP with a pH-sensitive Poly 4-vinylpyridine P4VP block. Applying the Breath Figure method casting (minute time scale process), this diblock copolymer allows to obtain a micro porous honeycomb film while a wall nano-structuration due to self-assembly of diblock copolymer is observed. Findings: The pH-triggered wettability is studied and correlated with the morphology evolution of P4VP nano-domains investigated by AFM in a liquid cell. Indeed, a nano-dots to nano-rings/donuts transition is highlighted when decreasing the pH below the pKa of the P4VP. This nano "sea Anemone" shape transition induces the macroscopic changes of the wettability of a hierarchically self-organized honeycomb film, explained by the protonation of P4VP chains inducing electrostatic repulsion and then hydrophilic surface. (C) 2020 Elsevier Inc. All rights reserved.