pH-sensitive wettability of polystyrene-b-poly(4-vinylpyridine)(PS-b-P4VP) self assembled films, exhibiting superoleophobicity under water and hydrophilicity at low pH value, and oleophobicity under water and hydrophobicity at neutral condition, has been realized. The wettability properties resulted from the surface topological and chemical transition, which were confirmed by in situ AFM measurements under water at different pH. At low pH, P4VP chains, which were confined in the hexagonal-packed nanodomains, got protonated into a swollen state, while at high pH, P4VP chains were deprotonated into a collapsed state. The reversible protonation/deprotonation procedure on the molecular scale leads to surface topological and chemical transition, thereby pH-sensitive wettability. pH-sensitive wettability of polystyrene-b-poly (4-vinylpyridine) (PS-b-P4VP) self assembled films, exhibiting superoleophobicity under water and hydrophilicity at low pH value, and oleophobicity under water and hydrophobic at neutral condition, has been realized . The wettability properties resulted from the surface topological and chemical transition, which were confirmed by in situ AFM measurements under water at different pH. At low pH, P4VP chains, which were confined in the hexagonal-packed nanodomains, got protonated into a swollen state , while at high pH, ​​P4VP chains were deprotonated into a collapsed state. The reversible protonation / deprotonation procedure on the molecular scale leads to surface topological and chemical transition, thus pH-sensitive wettability.