The town was established in the late 19th century when opal was discovered. In 1889 four kangaroo shooters were hired to reduce kangaroo numbers on the Momba Station. The roo shooters found opals and realising their potential value sent them off to Adelaide for valuation. Within the year a small settlement had come into existence and White Cliffs opals were available on markets in Britain, the Continent and the USA. By 1897 White Cliffs had grown to a point where there were about 1000 people. At its height around 1898-1900, White Cliffs was home to an estimated 5000 people and in today's terms sold millions of dollars worth of opal. Building materials were scarce and expensive and the heat in summer was oppressive. And, around 1894, miners started converting their old shafts into homes. Today there are around 140 "dugouts" (underground homes), which are as comfortable and modern as houses in other towns. Right now White Cliffs population depends on seasons and is somewhere between 100 and 400. From the air, White Cliffs looks like a moonscape with an estimated 50,000 disused diggings which look like small craters. In 1987 the production of opals from the White Cliffs fields was estimated to be $150 million. Remarkable opals have been found, such as the White Cliffs opal "pineapples" and opalised shells. By far the most unusual was the opalised remains of a nearly 2 metre long plesiosaur, believed to be around 100 million years old.

White Cliffs was chosen for building the solar power station because of the highest insolation in New South Wales. In 1981 the solar power station was constructed by a team from Australian National University. At that time White Cliffs had no electrical grid connection and the station provided electricity to the town. The station consisted of fourteen three-metre parabolic dishes, each covered by more than 2000 mirrors and mounted on a heliostatic mounting. The dishes each focussed the sun's rays on a collector, where water was boiled. The resulting steam drove a steam engine, delivering up to 25kWe. In 1996, following grid connection of the township, the station was converted to photovoltaic. The dishes were resurfaced, and the original collectors each replaced by a cluster of 16 water-cooled photovoltaic cells. In its new form, the station delivers up to 45kWe. The steam engine, batteries, and diesel generator were removed, and the output fed into the grid. The grid connected power station ran for around 6 years, generating valuable data on the long-term performance and efficiency of the modules. The power station ceased operation in December 2004 and has been resumed by the owner of the site.