He will also advise Venezuela against being a "puppet" of Cuba and say the USA administration is creating a path to the first fully democratic hemisphere in history.
The other European Union lawmakers expelled alongside Gonzalez included Jose Ignacio Salafranca and Gabriel Mato Adrover of Spain, Esther de Lange of the Netherlands and Paulo Rangel of Portugal.
Juan Guaido, the president of Venezuela's National Assembly who says he's the rightful leader of the country, has focused attention on emergency shipments of food stalled in the Colombian border town of Cucuta.
Guaido wrote on Twitter the lawmakers had been "deported by an isolated and increasingly irrational regime". President Nicolas Maduro government has refused to take in the aid thus far, saying it could justify foreign interference in the country's domestic affairs.
Food supplies, hygiene kits and nutritional supplements have been stockpiled near the Venezuelan border in Cucuta, Colombia. Through the months-long crisis, the military has largely remained loyal to Maduro.
"If it doesn't enter on the twenty-third, it will enter on the twenty-fourth, it will enter on the twenty-fifth" of February, he said.
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The Duchess of Cambridge wore a white one-shoulder Alexander McQueen gown and Jimmy Choo heels to the event. Earlier in the day, Kate wore a Dolce and Gabbana suit for a mental health in education conference.
Mr Maduro, who denies the existence of a humanitarian crisis, dismisses the opposition moves as a "political show" and a cover for a USA invasion.
Millions of people have already fled the border to seek a better life as a food and medicine shortage cause a major crisis.
"Venezuela is preparing for the humanitarian avalanche", Mr Guaido told about 4,000 supporters clad in white T-shirts and green scarves who gathered Saturday to sign up as volunteers.
Maduro is now refusing to allow in the food, medicine and other supplies.
While he said the United States is keeping all options on the table, Bolton added there would be "no effort to use military force to deliver the humanitarian assistance" that the Venezuelan government has refused to allow into the country.
But Venezuela's opposition leader Juan Guaido has called for crowds to converge on the border to collect the aid.