Top seed Roger Federer begins against Colombia's Alejandro Falla, while Nadal plays Kei Nishikori of Japan.
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The 23-year-old doubles specialist, ranked 113th in singles, will next play Colombia's Alejandro Falla.
Falla admitted the nerves had got to him as he prepared to serve for the match.
The tale took another twist when Falla called the trainer to attend to an apparent groin injury.
And the six-time champion hit top form in the deciding fifth set as Falla's fire finally died out.
He begins his campaign against Colombia's Alejandro Falla, the man who took him to five sets at Wimbledon in 2010.
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Falla, the world number 60, served for the match at 5-4 in the fourth set, but top seed Federer dug deep.
Alistair Martin was second in the category, with Alex Falla 10 seconds behind in third and Alex Wilson in fourth place.
But Falla shone on tennis's biggest stage, mixing slice with power off the backhand and hitting a string of crunching forehand winners.
The Frenchman edged out Colombia's Alejandro Falla 7-6 7-6 in intense heat.
Still, the danger lurked as Federer saved a break point in the very next game, but come the tie-break, Falla's challenge completely evaporated.
Elsewhere, Juan Martin Del Potro eased past Colombia's Alejandro Falla 6-2 6-2 to set up a third round clash with France's Michael Llodra.
Mai-Lea Falla, seven, a pupil at Vale Junior School, suffered a severe head injury when she was hit in Summerfield Road last November.
The report into the tendering process for a clinical block at the Princess Elizabeth Hospital was ordered after the bid by RG Falla was withdrawn.
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He deserved his chance to serve for the win at 5-4, but Federer, playing in his 57th Wimbledon match to Falla's ninth, kept his cool.
Federer claimed the first mini-break, netted another forehand to let Falla off the hook, but then won four points in a row to take the set.
Colombian Alejandro Falla handed victory to Bulgarian 26th seed Grigor Dimotrov while Germany's Florian Mayer , seeded 28, quit during his clash with Denis Istomin of Uzbekistan.
The Wales Audit Office (WAO) was asked to carry out an investigation following concerns the Policy Council had used its influence to encourage RG Falla to withdraw.
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Drawing Falla in the first round at his favourite tournament seemed like the perfect cure for his recent malaise: the Colombian had won only three matches in five previous visits to Wimbledon.
With Falla still treading gingerly between points, the tide appeared to have turned, but the Colombian stunned the Centre Court crowd yet again by breaking in the first game of the fourth.
And Deputy Stuart Falla said if the standard of living in the island was to continue at the same level, businesses would need specialist labour and Guernsey had to find the right balance.
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In the remaining second-round matches to be completed, Julien Benneteau won 6-0 in the fifth set to edge past Colombia's Alejandro Falla, while Florent Serra needed four tight sets to eliminate Romania's Victor Hanescu.
Eighth seed Fish was less happy to play in the scorching afternoon heat, complaining about the timeouts that Colombian opponent Alejandro Falla took for treating cramps before sealing a 7-6 (7-4) 6-3 7-6 (8-6) victory.
Federer had beaten Falla in straight sets in both of their previous meetings but was almost made to pay for a poor first set, which saw the top seed make a remarkable 21 unforced errors.
The 28-year-old's usually-impeccable forehand was malfunctioning badly and he survived break points in games three and five before more mistakes and a net cord saw him hand Falla a chance to serve for the set at 6-5.
Federer's performance, by contrast was curiously flat, and yet even when Falla broke for a 6-5 lead in the first set, there was a sense that the six-time champion would find a way to respond to the challenge.
After more downpours forced the players off for an hour in game two of the third set, Federer returned with renewed vigour to break in game three and serve out the match after some dogged resistance from Falla.
Serving for a two-set lead at 5-4, Falla faltered for the first time, but Federer was unable to take advantage, two break points slipping by before the Colombian forced his opponent off court and put away an easy volley on his fourth set point.
Having broken Pete Sampras's Grand Slam record at the All England Club last year, Federer is now looking to equal the American's haul of seven Wimbledon titles, but for long periods against left-hander Falla, it looked like his challenge might crumble on day one.
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