The Three Lions take on African side DR Congo in their last 32 tie on Wednesday (01.07.26) and the winger explained that the team have been diligent with their practice from 12 yards given the national team's miserable record from the spot.
Madueke said: "Just like all phases of play, we're taking it extremely seriously.
"As you go into knockout football it's something that becomes more prominent in the games, so like every part of our game we want to be at the highest level when it comes to that."
Asked if he would take a penalty, the Arsenal star said: "Yeah, for sure. I'm always open to take a penalty.
"At the end of the day it comes down to the coach's decision and what he wants and what he thinks is best for the team, but from my side I'm always ready."
Madueke is competing with club team-mate Bukayo Saka for a spot in Thomas Tuchel's team but insists that the pair have a close relationship.
He said: "Obviously it's well documented that we're very close, so normally it should be a little bit strange but it's not. I feel like it doesn't really affect our relationship whatsoever.
"I feel like we want the best for each other when each other plays because at the end of the day that means that if he plays well, I play well, then England and Arsenal have a better chance of winning.
"In terms of how we differ, I think I thrive in space and he thrives in congestion."
Madueke insists that the competition with Saka helps him to maintain a high level.
The forward said: "I feel like you always have to be at the highest level because you know you have a top player waiting and biting at your heels to try and get in the team.
"I think that type of healthy competition is good but playing for Arsenal and playing for England you don't really need anyone else to keep you at the highest level. You know that that's a requirement."