The defender, who joined from Osasuna, came on during the second half of the Reds’ 3-2 pre-season defeat to AS Monaco.
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Having only begun training with Liverpool earlier this week, Munoz completed his first 30 minutes for the club.
The Spain World Cup winner will now look to build fitness and continue adapting to life at Anfield.
“Very happy to debut with Liverpool FC in front of our fans,” Munoz posted on social media.
“Heartfelt thanks for all the support. We will continue to work hard to keep improving and growing.
“Up the Reds!”