Rodriguez came on for Cristiano Ronaldo in the second half at the Santiago Bernabeu and found the back of the net in the 80th minute.
Real could be without the world's most expensive player Gareth Bale and defender Pepe in the first leg due to injuries.
Real Madrid manager Carlo Ancelotii on Sunday ruled out any further signings before the end of the month.
World Cup-winning goalkeeper Manuel Neuer and Champions League-winning forward Cristiano Ronaldo are in a three-player contest to win UEFA's best player in Europe award.
Ronaldo struck twice as a rampant Real Madrid side, featuring the most expensive strike force ever assembled, powered to a 2-0 win over Sevilla.
"He's not leaving, he's a Real Madrid player. He has a contract until June 30, 2015 and that's all there is to say," Ancelotti said.
Rodriguez, after moving from Monaco will be in the starting lineup for the European champions against Sevilla.
Sevilla and Real Madrid will play for their first title of the new football season when the two Spanish clubs contest the European Super Cup in Cardiff.
Real Madrid are expected to field the world's most expensive strikeforce when they play Sevilla in the UEFA Super Cup on Tuesday.
Rodriguez hopes the scoring streak that earned him the Golden Boot award continues after his move to European champion Real Madrid.
Real Madrid's Welsh star, Bale is looking forward to returning 'home' next week when his side take on Sevilla in the European Supercup.