The Venezuelan is taking charge of his first match at the World Cup after being selected as one of 36 referees at the tournament in Qatar.
The 39-year-old is considered to be one of the top referees in South America - taking charge of matches in the Copa America, Copa Libertadores, Copa Sudamericana and South American World Cup qualifiers.
He referees professional in Venezuela’s top flight, where he took charge of nine matches before the league paused for the World Cup.
In those matches, however, Valenzuela showed red cards in seven of them, as well as an array of yellow cards.
England’s opening game against Iran was refereed by the Brazilian Raphael Claus.
England did not receive a single booking as Gareth Southgate’s side won 6-2.
Meanwhile, Jordan Pickford said he is hoping England get fair treatment from officials after boss Southgate said he was “worried” that his side had been used as an example during pre-World Cup referee meetings.
England were denied what looked like a clear spot-kick when Harry Maguire was grabbed by Rouzbeh Cheshmi early on in their victory.
The VAR decided not to intervene but later alerted the referee to a tug on a shirt in the England box which resulted in Mehdi Taremi scoring a last-gasp penalty, while a similar offence resulted in a spot-kick in Argentina’s shock defeat to Saudi Arabia on Tuesday.
Fifa referees committee chairman Pierluigi Collina had singled out England during a pre-tournament briefing – also open to the media – showing a clip of Kalvin Phillips blocking to create space in the box for Maguire to score in England’s 5-0 World Cup qualifying win over Albania last year.
The Italian said such a goal would be disallowed at the World Cup and Southgate has been left with concerns about the potential ramifications of England being the team highlighted ahead of the finals.