The hemibond is a nonclassical covalent bond formed between a radical (cation) and a closed shell molecule. The hemibond formation ability of water has attracted great interest, concerning its role in ionization of water. While many computational studies on the water hemibond have been performed, clear experimental evidence has been hardly reported because the hydrogen bond formation overwhelms the hemibond formation. In the present study, infrared photodissociation spectroscopy is applied to (H2O-Krn)+ (n = 1-3) radical cation clusters. The observed spectra of (H2O-Krn)+ are well reproduced by the anharmonic vibrational simulations based on the hemibonded isomer structures. The firm evidence of the hemibond formation ability of water is revealed. -Close-