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On December 31, 2001, Valero completed its acquisition of Ultramar Diamond Shamrock.

In June 2001, Valero acquired the Huntway Refining Company, along with two asphalt plants on the West Coast. The company also began retailing gasoline under the Valero brand. In 2000, Valero purchased ExxonMobil's Benicia, California, refinery and interest in 350 Exxon-branded service stations in California, mainly in the San Francisco Bay Area. In 1998, it then acquired a Paulsboro, New Jersey, refinery, the company's first outside of the Gulf Coast area. In May of that year, the firm acquired Basis Petroleum, which left it with four refineries in Texas and Louisiana. At the same time, the remaining divisions, which consisted of natural gas operations, merged with a wholly owned subsidiary of Pacific Gas and Electric Company. In 1997, Valero Energy Company spun off its subsidiary, Valero, to its stockholders. In May 1985, Valero Refining and Marketing Company was born from Valero's subsidiary, Saber Energy, Inc. Valero acquired Corpus Christi Marine Services Company ("CCMS"), a small barge company in Corpus Christi, Texas in April 1981 when it purchased a stake in Saber Energy Inc. The name Valero comes from Mission San Antonio de Valero, the original name of the Alamo. Valero took over the natural gas operations of the LoVaca Gathering Company, later renamed the Valero Transmission Company.

Valero was created on January 1, 1980, as the successor of Coastal States Gas Corporation's Subsidiary, LoVaca Gathering Company. A Fortune 500 company, before the 2013 spinoff of CST Brands, Valero was one of the United States' largest retail operators with approximately 6,800 retail and branded wholesale outlets in the United States, Canada, United Kingdom, and the Caribbean under the Valero, Diamond Shamrock, Shamrock, Beacon, and Texaco brands. Throughout the United States and Canada, the company owns and operates 15 refineries, and one in Wales, with a combined throughput capacity of approximately 3 million barrels (480,000 m 3) per day, 11 ethanol plants with a combined production capacity of 1.2 billion US gallons (4,500,000 m 3) per year, and a 50-megawatt wind farm. It is headquartered in San Antonio, Texas, United States. Valero Energy Corporation is an American-based downstream petroleum company mostly involved in manufacturing and marketing transportation fuels, other petrochemical products, and power.