Colombian attacking midfielder James scored twice as Madrid put Deportivo La Coruna to the sword in a 6-2 demolition on Wednesday.
Playing in the absence of Cristiano Ronaldo and Gareth Bale, James - who scored in the 3-2 Clasico defeat last week - netted in each half to help Madrid stay level with titleholders Barca.
Barca and Madrid are locked on 78 points atop the table, though the latter have a match in hand in their pursuit of a first La Liga trophy since 2012.
"I feel happy and really satisfied," James said. "We played very well, with high intensity and desire. What we did out there was positive.
"We have five cup final games in La Liga, which we have to go into with hunger, and we also have to think about the Champions League.
"Regardless of who plays, the team always play well. When we have such opportunities, we have to do well as we did."
James has found regular game time hard to come by under head coach Zinedine Zidane.
James' frustrations, however, have not impacted his performances after he, Lucas Vazquez, Isco and Alvaro Morata helped Madrid to victory midweek.
"Maybe it's because we play a little and when we have those small opportunities we can do good things," he said.
"The two teams [first XI and fringe players] always play well."
Madrid are back at the Santiago Bernabeu on Saturday, hosting Valencia.