The high-flying Djokovic's second-round opponent will be Slovenian Blaz Kavic, who downed injury-plagued fading former world No. 1 and two-time Grand Slam titlist Lleyton Hewitt of Australia 7-6 (7-2), 6-3, 6-7 (4-7), 6-3.
Federer, meanwhile, posted a 6-2, 7-5, 6-3 win over German Tobias Kamke to improve his Grand Slam win-loss record to 233-35. The amazing Swiss icon is now tied with Jimmy Connors (233-49) for the most Grand Slam wins in the Open Era (since 1968).
"That's a big one, because that was longevity," Federer said. "Jimmy is obviously one of the greats of all time and was around for 20 years."
The 16-time Grand Slam winner Federer, who captured the French Open title in 2009 to complete his career Grand Slam, lost to six-time champion Rafael Nadal in last year's finale here. Federer is a four-time French Open runner-up to his great rival Nadal.
Federer is looking to become the first 30-or-over man to win a Grand Slam title since Andre Agassi won the 2003 Australian Open at 32 years, 272 days. Andres Gomez was the last man to win Roland Garros over the age of 30, when he won the 1990 title at 30 years, 130 days.
Up next for Federer will be Ukrainian Adrian Ungur.
Seventh-seeded former Wimbledon runner-up and recent Madrid Masters finalist Tomas Berdych of the Czech Republic blew past Israeli Dudi Sela 6-3, 6-4, 6-1, while 11th-seeded gritty Frenchman Gilles Simon doused promising young American Ryan Harrison 3-6, 7-5, 6-4, 6-1, and 10th-seeded towering American John Isner continued his fine play on red clay this year with a 6-3, 6-4, 6-4 victory over Brazilian Rogerio Dutra Silva. The 6-foot-10 Isner is now 7-3 on crushed red brick this season and will encounter Frenchman Paul-Henri Mathieu in round two.
Fifteenth-seeded Spaniard Feliciano Lopez exited the draw while trailing France's Florent Serra 0-5 in the first set, citing a side muscle injury.
Other seeded winners were No. 20 Spaniard Marcel Granollers, No. 22 Italian Andreas Seppi, No 24 German Philipp Kohlschreiber, No. 25 Aussie Bernard Tomic, No. 28 Serb Viktor Troicki, and No. 31 South African Kevin Anderson. Seppi subdued fading former top-five star and two-time French Open semifinalist Nikolay Davydenko of Russia 6-3, 7-6 (7-5), 7-5.
Belgian David Goffin erased 23rd-seeded Czech Radek Stepanek 6-2, 4-6, 2-6, 6-4, 6-2, while the aforementioned Ungur surprised former Wimbledon runner-up and two-time French Open semifinalist David Nalbandian of Argentina 6-3, 5-7, 6-4, 7-5.
American feel-good story Brian Baker continued his recent winning ways with a 6-3, 7-6 (7-1), 7-6 (7-5) victory over Belgian Xavier Malisse. The Nashville, Tenn. native Baker, who basically had been out of tennis since the mid 2000s because of a bevy of injuries, including a reconstructed elbow, was a surprise first-time ATP finalist in Nice last week.
Baker should have his hands full with the pesky Simon in the next round.
Several other men landed in the second round, including French crowd favourites Arnaud Clement, Michael Llodra and Mathieu, and American Jesse Levine, who topped German Benjamin Becker 7-5, 6-2, 6-4. The 34-year-old former Aussie Open finalist Clement was leading Alex Bogomolov Jr. 6-2, 3-6, 4-6, 7-5 (7-2), 5-4 when the Russian retired from the bout, while Mathieu came from two-sets-to-love down to overcome speedy German Bjorn Phau 2-6, 4-6, 6-4, 6-3, 6-0.
Clement and fellow Frenchman Fabrice Santoro hold the record for the longest-ever French Open match in the Open Era, at 6 hours, 33 minutes, in a tussle won by Santoro in five sets, including a 16-14 fifth, back in 2004.
Sixteenth-seeded Alexandr Dolgopolov was tied with fellow Ukrainian Sergiy Stakhovsky, 7-6 (7-4), 4-6, 6-7 (4-7), 6-3, when play was suspended because of darkness.
The first round is scheduled to conclude on Tuesday, including matches for a second-seeded Nadal, fourth-seeded Andy Murray and sixth-seeded David Ferrer.
Nadal, seeking a third straight and Open Era-record seventh French Open title, will open his 2012 Parisian stay against Italian Simone Bolelli, while the three-time Grand Slam finalist Murray will encounter Japan's Tatsuma Ito and Ferrer will take on Slovak Lukas Lacko.
The 10-time major titlist Nadal, who is a remarkable 45-1 lifetime at Roland Garros, has lost to Djokovic in the last three Grand Slam finals.
The 2012 Roland Garros titlist will earn $1.57 million.