Octane became a significant, and practical compound shortly after the discovery of petroluem during the Industrial Revolution replaced traditional fuels such as animal fats and whale oil. To start off the rush for fossil fuels as an energy source, Colonel Edwin L. Drake drilled the first oil well at Titusville, Pennsylvania, in 1859. Little did he realize that, in the future, such a demand would eventually be placed on fossil fuels that their abundance would nearly run out and their use would pose an environmental problem for the entire world. Yet gasoline, which contains octanes, was not used initially. Kerosene was the most popular source of refined fuel because it burned well in oil lamps. However, when the electric light was invented, oil lamps and kerosene became mostly obsolete, opening the door for gasoline to take centerstage. With the development of the "horseless carriage" (gas-powered engines), gasoline became a hot commodity.

Because the gasoline industry was growing, more efficient ways of refining the raw petroleum were demanded. So, William Burton invented pyrolytic cracking (high temperatures) at Standard Oil of Indiana. This process heats the heavier molecules of kerosene to 700 degrees Celsius until they "crack" into the smaller hydrocarbons of gasoline. This discovery by Burton led to many more revolutions in "cracking" and refining that were badly needed by the gas industry (Uses).

As car engines grew bigger, more efficient internal combustion engines were manufactured, which did not coincide with the dawdling gas industry. Gasoline burned unevenly, causing "knock," or pre-ignition of the engine fuel, which causes noise and even damage to the engine. Therefore, tetraethyl lead [(C₂H₅)₄Pb] was used as an additive in gas to prevent knock. Eventually, in 1960, up to 3 grams of lead were added to a gallon of gas. However, lead emissions caused environmental problems; so, catalytic converters were invented to help the car exhaust system maintain its pollution output. But the lead was too great an adversary for the converters, so lead additives have been limited by laws and regulations implemented over the years, causing the gas industry to raise prices to finance more expensive and tedious methods of refining petroleum, like catalytic synthesis and high-pressure hydrogenation.