Although the pH-response of poly(vinylpyridine)-based systems is well-known and indeed used in several biomedical applications, the impact of temperature on the properties of this polymer has not been investigated in detail so far. Herein, we demonstrate the temperature-responsiveness and switchable wettability of two poly(4-vinylpyridine) coatings, mimicking the behavior of materials with lower critical solution temperature. The thermal response of P4VP spin-coated films, solvent cast on a glass, is weaker than that observed for P4VP-grafted brushes, fabricated via polymerization from an oligoperoxide grafted on an amino-silanized glass. Both the P4VP coatings exhibit a temperature dependence of the water contact angle with a well-defined transition at 13–14 °C. This transition is absent at acid pH levels wherein almost all pyridyl groups are protonated. The P4VP-grafted brushes were used to examine the impact of temperature on the surface morphology and protein adsorption. The coating surface, recorded with atomic force microscopy, evolved noticeably at alkaline pH, from being relatively smooth at 10 °C to structured and rough at 20 °C. In turn, at acid pH levels, flat surfaces with rare elevations were observed at both temperatures. The adsorption of bovine serum albumin and human fibrinogen was observed with fluorescence microscopy to be significantly more efficient for temperatures above the transition, indicating that P4VP coatings can act as a noteworthy switching material.