No. 6 Li Na , who became Asia's first grand slam singles champion at Roland Garros at the French Open, in 2011, lost to Radwanska in the final of the Sydney International last week, but the Chinese star opened up in Melbourne with a 6-1 6-3 triumph against Sesil Karatantcheva of Kazakhstan.
Rome is a key warm-up for the French Open at Roland Garros, the year's second Grand Slam, which starts on May 26.
But he had not won on the ATP Tour since claiming the French Open at Roland Garros last June as Djokovic has dominated.
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Djokovic, who helped Serbia reach the quarterfinals of the World Group of the Davis Cup for the first time in the week following his Dubai success, will next target the Masters events in the United States in early spring before turning his attentions to the French Open at Roland Garros as he bids to extend his grand slam tally.
The 26-year-old is hoping to add to his record seven French Open titles at Roland Garros in June.
Federer, who will defend his French Open title at Roland Garros next month, looked woefully out of form and made under 50 per cent of his first serves as he slumped to defeat in just over two hours.
The French Open at the iconic Roland Garros stadium is a competition rich in history and drama, and 2010 is set to be no different.
Li made history 20 months ago, lifting the Coupe Suzanne Lenglen in Paris to become the first Asian player to win a Grand Slam singles title Roland Garros, better known as the French Open.
He has always been generous in his praise of Sampras, who never won at Roland Garros but triumphed twice at the Australian Open and holds the record for winning eight successive Grand Slam finals.
Her older sibling Venus, who is in the same half of the draw, bounced back from her early exits at the French Open and Wimbledon by thrashing Roland Garros runnerup Sara Errani 6-3 6-1 in her delayed first-round match.
Her maiden slam means all four majors are in the hands of first-time winners for the first time in history, following wins by Li Na, Petra Kvitova and Samantha Stosur at Roland Garros, Wimbledon and the U.S. Open last year, respectively.
Roland Garros followed the examples of the U.S. Open and the Australian Open on Monday by increasing the prize money for singles champions and players who are eliminated earlier in the tournament.
However, he made it to the semifinals at Roland Garros in June and also the last eight at January's Australian Open and Wimbledon in July.
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Nadal's victory here last year came in Djokovic's absence, and the Spaniard subsequently lost to him in Madrid and Rome before beating Roger Federer in the French Open final for a record-equaling sixth title at Roland Garros.
The news is a another blow for the Spaniard who, despite being used to arriving at The Queen's Club as the newly crowned French Open champion, suffered his first-ever defeat at Roland Garros losing to Sweden's Robin Soderling in a last 16 tie.
Last year she beat 2013 Australian Open champion Victoria Azarenka in the Stuttgart final before claiming her Roland Garros triumph.
Belgian former world number one Henin is returning to Roland Garros for the first time since 2007 when she won the fourth of her French Open titles.
Li lost the 2011 Australian Open final to Kim Clijsters but won her first Grand Slam title at Roland Garros a few months later, beating Francesca Schiavone.
They have not met since Nadal won last year's French Open final -- his record seventh title on the red clay of Roland Garros -- and the Spaniard holds a 19-14 career advantage in their matches.
Nadal has lost only once at Roland Garros since his first appearance in Paris in 2005, when he began a run of four successive French Open titles, while Monaco's best effort is a fourth-round defeat in 2007.
Federer was using the tournament as a warm-up to the French Open, where the Swiss ace will be looking to defend his title when the tournament starts at Roland Garros on May 23.
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