The 25-year-old won a bronze medal for Serbia with victory over James Blake at Beijing 2008, and he is hoping to climb to the top step of the podium when the medals are decided at Wimbledon next weekend.
He has been enjoying the Olympic spirit since arriving in London, and he harked back to the Games' classical traditions when contemplating what the competition means.
Djokovic said: 'The majority of athletes cannot remove the smile from their faces. It's just an excitement that is like no other.
This is the most recognised event in the history of sport. In the past, when you won an Olympic gold, you were considered immortal and you got eternal glory, and I don't think it has changed much really.Novak Djokovic
'This is the most recognised event in the history of sport. In the past, when you won an Olympic gold, you were considered immortal and you got eternal glory, and I don't think it has changed much really.'
Djokovic's Olympics will begin at the Opening Ceremony when he carries Serbia's flag into the Olympic Stadium, before a first-round clash with Italy's Fabio Fognini on Sunday.
'It is a unique experience, maybe once in a lifetime, and I will try to enjoy every single moment of it,' he said.
'I'm aware there are so many other athletes who are equally deserving to be in my position and it is an experience that will hold a special place in my heart.'
Djokovic took over as world number one after winning Wimbledon last year but was usurped by Roger Federer exactly a year later courtesy of the Swiss star's triumph over Andy Murray at the All England Club.
Federer is among those in action on the first day, with the top seed taking on Colombia's Alejandro Falla, while fellow Wimbledon champion Serena Williams meets Jelena Jankovic in the women's Singles.
British pair Anne Keothavong and Elena Baltacha also play their first Singles matches, with the former facing a tough task against eighth seed Caroline Wozniacki of Denmark while Baltacha meets Hungary's Agnes Szavay.
In the Doubles, Andy and Jamie Murray are among those in action as they face Austrian pair Jurgen Melzer and Alexander Peya.