Wide-area surface decontamination is essential during the sudden release of radioisotopes to the public, such as nuclear accidents or terrorist attacks. A spray coating composed of a reversible complex between poly (vinyl alcohol) (PVA) and phenylboronic acid-grafted poly (methyl vinyl ether-alt-mono-sodium maleate) (PBA–g–PMVE–SM) was developed to remove radioactive cesium from surfaces. The simultaneous spay of PVA and PBA–g–PMVE–SM aqueous polymer solutions containing Cs adsorbent to contaminated surfaces resulted in the spontaneous formation of a PBA–diol ester bond-based gel-like coating. The Cs adsorbent suspended in the gel-like coating selectively removed Cs-137 from the Cs-contaminated surface. The used gel-like coating were removed from surfaces by simple water rinsing. This recovery way has advantages compared with costly incineration to remove the organic materials for final disposal/storage of the radioactive waste. Thus, our spray coating is suitable for practical wide-area surface decontamination. In radioactive tests, the hydrogel containing Cs-adsorbent showed substantial Cs-137 removal efficiencies of 96.996% for painted cement and 63.404% for cement, which are 2.33 times better than the values for the commercial surface decontamination coating agent DeconGel.