Coal was the first fossil fuel to be used by humans. It is also the most abundant, the cheapest, and by far the dirtiest. Coal industry has a long history in Russia. Some of the oldest mines in the FSU are over two centuries old; they are located in Ukraine today, mainly in the Donbass basin (Lugansk and Donetsk Oblasts), which partially extends into Russia's southwestern region of Rostov-on-Don. The old-fashioned underground mines of Ukraine and Russia are among the most dangerous in the world, with annual fatalities averaging a few hundred. These result from methane explosions and mine collapses. Modern open-pit and strip mines are common in Siberia, especially in the huge Kansk-Achinsk basin, which alone contains over 50% of Russia's coal. Over 65% of coal in Russia is produced now in open-pit mines. This method is safer for the miners, but results in much surface damage. In the Kuzbass and Donbass areas, however, mining continues primarily underground; this produces better-quality coal for making steel, but also leads to numerous accidents.

The total proven coal reserves of Russia are second in the world, after those of the United States—about 200 billion metric tonnes, with 114 billion in Kansk-Achinsk, 57 billion in the Kuznetsk basin of central Siberia, and 9 billion in the Pechora basin in the northeastern European part. The United States has about 240 billion metric tonnes in reserves, the largest on the planet. Only Ukraine and Kazakhstan have substantial coal reserves in the FSU besides Russia. Traditionally coal was used in steel making, other metallurgy, the chemical and fertilizer industries, and electricity generation. However, since 1980 natural gas has largely replaced coal as the main fuel in Russia's power stations. In present-day Russia, only 15% of all energy comes from coal, as compared to 23% in the United States. Because of the shift toward natural gas, there has been an improvement in air quality around big industrial centers. The leading producer of coal in the country is the Kuzbass basin (over 160 million metric tonnes [mmt] in 2003). The second largest producer is the Kansk-Achinsk basin (34 mmt), with the Pechora (13 mmt) and Russian Donbass (7 mmt) basins producing most of the balance. As in the United States, Russian coal companies maintain a lower profile than the petroleum producers do. Nevertheless, the largest coal mine in the country, Raspadskaya, had market capitalization of over $2 billion in mid-2007 and was ranked the 63rd largest company in the country. This mine alone can produce over 7.5 mmt of coal per year.

Many large coal-fired electric plants are located near the biggest open mines in Siberia (Surgut-2, Berezovo-1, Neryungrinskaya, Kharanorskaya, etc.). These stations each have a power generation capacity of between 4,000 and 6,000 megawatts (MW), comparable to that of the largest hydropower dams in the world. Each produces enough electricity to power a large city of a few million people, and millions of tons of carbon dioxide per year. RAO EES (United Energy Systems of Russia) was the monopoly that ran the country's electric grid until 2008 (now partially privatized and subdivided) and is one of the largest polluters in the world. It was the fifth largest company in Russia in 2008 in terms of market capitalization and is the largest unified electric grid in the world, stretching deep into most of the other FSU republics. It has since been reorganized, with independent energy companies created in different regions. Theoretically, this should lead to increased competition and lower tariffs for the consumers. So far, however, the results have not been very encouraging, with energy prices steadily rising between 10 and 15% per year. Russia produces about 6,000 kilowatt-hours per person per year; this equals the level of Germany or the United Kingdom, but it is quite a bit behind Australia (11,000) or the United States (14,500).

Russia ratified the Kyoto Protocol in 2004, after many years of dragging its feet. Because Russia's cumulative greenhouse emissions in the early 2000s were a lot lower than in 1990, owing to the economic downturn of the late 1990s, the country originally was in a position to gain a lot of money through the sale of carbon offsets to the EU. As of 2009, however, the country's emissions had climbed back almost to the 1990 level, so in the very near future Russia must either lower its emissions (which is highly unlikely) or start paying other countries for permits as mandated by the Kyoto agreement. Heavy reliance on coal and natural gas for energy generation will not help in the short term. However, Russia also has over 30 nuclear stations and is likely to start building more in the future
as a possible solution to the problem of carbon dioxide pollution.