Senior U.S. officials are traveling to Venezuela on Saturday to meet with the government of President Nicolás Maduro, according to people familiar with the matter, as the Biden administration steps up efforts to separate Russia from its remaining international allies amid a widening standoff over Ukraine.

The trip is the highest-level visit by Washington officials to Caracas, Venezuela’s capital, in years. The United States broke off diplomatic relations with Mr. Maduro and closed its embassy in Caracas in 2019, after accusing the authoritarian leader of electoral fraud. The Trump administration then tried to topple Mr. Maduro’s government by sanctioning Venezuelan oil exports and the country’s senior officials, and by recognizing the opposition leader, Juan Guaidó, as Venezuela’s lawful president.

Mr. Maduro responded to the sanctions by seeking economic and diplomatic help from Russia, as well as from Iran and China. Russian energy companies and banks have been instrumental in allowing Venezuela to continue exporting oil, the country’s biggest source of foreign currency, despite the sanctions, according to U.S. officials, Venezuelan officials and businessmen.

Russia’s invasion of Ukraine has prompted the United States to pay closer attention to President Vladimir V. Putin’s allies in Latin America, which Washington believes could become security threats if the standoff with Russia deepens, according to current and former U.S. officials who spoke on the condition of anonymity to discuss sensitive policy matters.

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