Edmund, who took to the court shortly after England's World Cup quarter-final victory against Sweden, was in inspired form early in the match.
Edmund gave the crowd something to cheer for, taking the first set against the 12-time Grand Slam champion before Djokovic prevailed, 4-6 6-3 6-2 6-4.
At the end of the match, Djokovic eschewed his now customary demonstration of love for the fans, instead performing a leaping fist-pump towards his box.
Djokovic received a time violation during the third set, met by widespread applause, but the intense atmosphere only seemed to further galvanise the former world No 1.
"My interaction with the crowd, I thought had good things and not that great things".
A couple of guys were were coughing and whistling while I was bouncing the ball more or less until the end of the match.
Talking about the "double-bounce" incident after the match, the three-time Wimbledon victor told the press: "I was 100 per cent convinced (of the double bounce) but everyone can make mistakes, it was a very important point. I just made him play an extra shot, got that crucial break in the ninth game that allowed me to win the match". It was not like this, definitely.
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"They kept on going, provoking".
"I'm going to show that I'm present, as well, that they can't do whatever they feel like doing". "If in real life it's hard to tell, then it's hard to tell for me when I'm scrambling". "I was extremely negative yesterday and just needed to come out with a very different state of mind and different approach today", he said. 'He has a very good team of people around him. "When you're at Centre Court, to have the crowd behind you is a great thing". "It was quite a odd decision from the chair umpire, but it happens".
"I was 100 percent convinced it was a double bounce in the fourth set, but anyone can make a mistake", Djokovic said. 'Kyle is a very nice guy.
Edmund ended up holding serve, but Djokovic broke at his next opportunity to make sure there will be no British players in the second week of the tournament. I think I put a decent level out on court'.
Djokovic had made his Wimbledon debut in 2005 at the age of 18, losing in the third round, and he was in the second week in 11 out of the next 13 years, winning three titles over Rafael Nadal and Roger Federer while losing in the final in 2013 to Murray.
"I would have maybe, looking back on it, liked to have been a little bit more aggressive at stages".
"If you were in my position, you would probably understand", said the 12-time major victor. "I think overall it's been more positive from my side".