The Serb was denied the honour of becoming the first man since 1969 to hold all four grand slam titles at once earlier this month when he lost the final in Paris to clay-court king Rafael Nadal.
Djokovic admits to being hurt by that near miss but is adamant that it will not be on his mind when he opens Centre Court this afternoon against Spain’s experienced Juan Carlos Ferrero.
“Yes, I was so close, and there was a slight disappointment after the match because I was aware of the chance that I had at Roland Garros,” he said. “But the day after I felt good about my tournament, about my achievement. It was the first time I had been in the finals of Roland Garros. That’s a step further from all these years that I’ve been playing in Paris.”
British No1 Andy Murray does not begin his latest tilt at winning a first grand slam until tomorrow, but there are still five home hopes taking part on the opening day.
Heather Watson, fresh from reaching the second round at Roland Garros and some encouraging displays in Eastbourne last week, faces Czech Republic’s Iveta Benesova, who at No55 is ranked 48 places above the Guernsey 20-year-old.
Australia-born Johann Konta begins her first Wimbledon since switching allegiance to Britain against American 28th seed Christina McHale, while Naomi Broady meets Lourdes Dominguez Lino. In the men’s draw, 18-year-old US Open junior champion Oliver Golding faces Russian world No93 Igor Andreev, while Josh Goodall plays Slovenian world No120 Grega Zemlja.
Men’s first round
■ N Djokovic  v J C Ferrero
■ R Federer  v A Ramos
■ D Nalbandian v J Tipsarevic 
■ E Gulbis v T Berdych 
Women’s first round
■ M Sharapova  v A Rodionova
■ K Clijsters v J Jankovic 
■ V Williams v E Vesnina
■ N Li  v K Pervak