While Djokovic won in straight sets, Serena erased three breaks in final set to stave off an upset bid by Heather Watson.
Dustin Brown stunned Rafael Nadal 7-5 3-6 6-4 6-4 in second round of Wimbledon 2015.
Nadal was humbled 7-5, 3-6, 6-4, 6-4 by dreadlocked German Dustin Brown, World No. 102, in second round.
Earlier, Andy Murray and Roger Federer cruised into Rd 3 after winning their respective matches.
The top seeded Indo-Swiss pair defeated Diyas and Zheng 6-2 6-2 in the opening women's doubles match.
Wimbledon's dress code states that players must dress in 'almost entirely white' during competitive matches.
In the bright sunshine in southwest Wimbledon, temperatures reached 35.7 degrees Celsius.
Djokovic will face Bernard Tomic while Serena will be up against Daniela Hantuchova.
Paes and Nestor quelled the challenge from the Serbian pair of Victor Troicki and Dusan Lajovic.
Kei Nishikori beat Italian Simone Bolelli in the first round.
Top seeds Novak Djokovic, Maria Sharapova, Stan Wawrinka, Serena Williams cruise on a very very hot day.
This video will show you how the tennis ball contracts in the immediate aftermath of being hit by a racket.
Defending women's champion Kvitova and former men's winners Federer and Nadal all won their first-round matches.
There is a "heat rule" in place but it applies only to the women's game if mercury reaches 30.1 degrees Celsius before the match.
Federer, Nadal and Murray storm into Rd 2; Kvitova starts title defence with domintaing win.
Defending champion Novak Djokovic fears he is becoming the victim of a smear campaign.
A seven-point statement has been signed against poor organisation and lack of transparency by the Spanish federation (RFET).
Djokovic only got onto grass courts ten days ago, in contrast to his rivals in build up to Wimbledon defence.
David Ferrer, seeded eighth, pulled out of Wimbledon 2015 due to a elbow injury.
Win at Halle and love-affair with Wimbledon grass gives Federer his best and perhaps last chance to win a Grand Slam.
Djokovic, seeded one, has not played a competitive match since losing to Stanislas Wawrinka in the French Open final.
Paes is the 47th player to reach a century of doubles partners.
In the semifinals, Sania Mirza-Martina Hingis will take on Caroline Garcia-Katarina Srebotnik.
Djokovic, seeking a third Wimbledon crown is the top seed in the third Grand Slam of the year.
Sania-Hingis will now face Hao-Ching Chan of Taipei and Flavia Pennetta from Italy in the quarterfinals.
Kyrgios withdrew from a tournament in Stuttgart earlier this month due to an elbow injury.
Roger Federer captured a fourth title this year after victories at Istanbul, Dubai and Brisbane to take his career haul to 86.
Paes and Nestor did not any break chance in the opening set while their rivals capitalised on the one offered.
Andy Murray's titles have come in alternate years -- 2009, 2011, 2013 and now 2015.
Both players held serve until Federer made a mini-break to go 4-3 up in the first tiebreaker.
World number two Roger Federer will now face Croatian giant Ivo Karlovic in the semi-final.
Leander Paes and his Canadian counterpart manged to tame their opponents to win the match with 72 points.
Andy Murray fended off some typically ferocious hitting by Spaniard Verdasco to win 7-5 6-4.
Kei Nishikori beat Dustin Brown 7-5 6-1 to set up a clash with Poland's Jerzy Janowicz.
Sania Mirza's regular partner Martina Hingis could not play in this tournament with Sania for some personal reasons.
Roger Federer comfortably beat Latvian Ernests Gulbis 6-3 7-5.