Liquid water cannot persist on the lunar surface. When exposed to solar radiation, water quickly decomposes through a process known as photodissociation and is lost to space. However, since the 1960s, scientists have hypothesized that water ice may be deposited by impacting comets or possibly produced by the reaction of oxygen-rich lunar rocks, and hydrogen from solar wind, leaving traces of water which could possibly persist in cold, permanently shadowed craters at either pole on the Moon. Computer simulations suggest that up to 14,000 km2 (5,400 sq mi) of the surface may be in permanent shadow. The presence of usable quantities of water on the Moon is an important factor in rendering lunar habitation as a cost-effective plan; the alternative of transporting water from Earth would be prohibitively expensive.

In years since, signatures of water have been found to exist on the lunar surface. In 1994, the bistatic radar experiment located on the Clementine spacecraft, indicated the existence of small, frozen pockets of water close to the surface. However, later radar observations by Arecibo, suggest these findings may rather be rocks ejected from young impact craters. In 1998, the neutron spectrometer on the Lunar Prospector spacecraft showed that high concentrations of hydrogen are present in the first meter of depth in the regolith near the polar regions. Volcanic lava beads, brought back to Earth aboard Apollo 15, showed small amounts of water in their interior.

The 2008 Chandrayaan-1 spacecraft has since confirmed the existence of surface water ice, using the on-board Moon Mineralogy Mapper. The spectrometer observed absorption lines common to hydroxyl, in reflected sunlight, providing evidence of large quantities of water ice, on the lunar surface. The spacecraft showed that concentrations may possibly be as high as 1,000 ppm. In 2009, LCROSS sent a 2,300 kg (5,100 lb) impactor into a permanently shadowed polar crater, and detected at least 100 kg (220 lb) of water in a plume of ejected material. Another examination of the LCROSS data showed the amount of detected water to be closer to 155 ± 12 kg (342 ± 26 lb).

In May 2011, 615–1410 ppm water in melt inclusions in lunar sample 74220 was reported, the famous high-titanium "orange glass soil" of volcanic origin collected during the Apollo 17 mission in 1972. The inclusions were formed during explosive eruptions on the Moon approximately 3.7 billion years ago. This concentration is comparable with that of magma in Earth's upper mantle. Although of considerable selenological interest, this announcement affords little comfort to would-be lunar colonists—the sample originated many kilometers below the surface, and the inclusions are so difficult to access that it took 39 years to find them with a state-of-the-art ion microprobe instrument.