We present the results of ALMA band-5 (~170 GHz) observations of the merging ultraluminous infrared galaxy, the Superantennae (IRAS 19254-7245) at z=0.0617, which has been diagnosed as containing a luminous obscured active galactic nucleus (AGN). In addition to dense molecular line emission (HCN, HCO+, and HNC J = 2-1), we detect a highly luminous (~6e4Lsun) 183 GHz H2O 3(1,3)-2(2,0) emission line. We interpret the strong H2O emission as largely originating in maser amplification in AGN-illuminated dense and warm molecular gas, based on (1) the spatially compact (<220 pc) nature of the H2O emission, unlike spatially resolved (>500 pc) dense molecular emission, and (2) a strikingly different velocity profile from, and (3) significantly elevated flux ratio relative to, dense molecular emission lines. H2O maser emission, other than the widely studied 22 GHz 6(1,6)-5(2,3) line, has been expected to provide important information on the physical properties of gas in the vicinity of a central mass-accreting supermassive black hole (SMBH), because of different excitation energy. We here demonstrate that with highly sensitive ALMA, millimetre 183 GHz H2O maser detection is feasible out to >270 Mpc, opening a new window to scrutinize molecular gas properties around a mass-accreting SMBH far beyond the immediately local universe.