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| Wimbledon Grass | Jul 7 2013 |
| 4 | Sabine Lisicki(23) - Williams(1) | 6-2 1-6 6-4 |
| 3 | Williams(1) - Kimiko Date-Krumm | 6-2 6-0 |
| 2 | Williams(1) - Caroline Garcia-Q | 6-3 6-2 |
| 1 | Williams(1) - Mandy Minella | 6-1 6-3 |
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| Roland Garros Clay | Jun 9 2013 |
| F | Williams(1) - Maria Sharapova(2) | 6-4 6-4 |
| SF | Williams(1) - Sara Errani(5) | 6-0 6-1 |
| QF | Williams(1) - Svetlana Kuznetsova | 6-1 3-6 6-3 |
| 4 | Williams(1) - Roberta Vinci(15) | 6-1 6-3 |
| 3 | Williams(1) - Sorana Cirstea(26) | 6-0 6-2 |
| 2 | Williams(1) - Caroline Garcia-WC | 6-1 6-2 |
| 1 | Williams(1) - Anna Tatishvili | 6-0 6-1 |
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| Rome Premier Clay | May 19 2013 |
| F | Williams(1) - Victoria Azarenka(3) | 6-1 6-3 |
| SF | Williams(1) - Simona Halep-Q | 6-3 6-0 |
| QF | Williams(1) - Carla Suarez Navarro | 6-2 6-0 |
| 3 | Williams(1) - Dominika Cibulkova(14) | 6-0 6-1 |
| 2 | Williams(1) - Laura Robson | 6-2 6-2 |
| 1 | Williams(1) | bye |
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| Madrid Premier | May 12 2013 |
| F | Williams(1) - Maria Sharapova(2) | 6-1 6-4 |
| SF | Williams(1) - Sara Errani(7) | 7-5 6-2 |
| QF | Williams(1) - Anabel Medina Garrigues-WC | 6-3 0-6 7-5 |
| 3 | Williams(1) - Maria Kirilenko(13) | 6-3 6-1 |
| 2 | Williams(1) - Lourdes Dominguez Lino-WC | 6-2 7-5 |
| 1 | Williams(1) - Yulia Putintseva-Q | 7-65 6-1 |
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| Fed Cup Play-off | Apr 20 2013 |
| | Williams - Sofia Arvidsson-swe | 6-2 6-1 |
| | Williams - Johanna Larsson-swe | 6-2 6-2 |
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| Best results: |
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| | | | Austr. O. | Roland G. | Wimbled. | US Open |
| 1998 | 2 | 4 | 3 | 3 |
| 1999 | 3 | 3 | | * |
| 2000 | 4 | | SF | QF |
| 2001 | QF | QF | QF | F |
| 2002 | | * | * | * |
| 2003 | * | SF | * | |
| 2004 | | QF | F | QF |
| 2005 | * | | 3 | 4 |
| 2006 | 3 | | | 4 |
| 2007 | * | QF | QF | QF |
| 2008 | QF | 3 | F | * |
| 2009 | * | QF | * | SF |
| 2010 | * | QF | * | |
| 2011 | | | 4 | F |
| 2012 | 4 | 1 | * | * |
| 2013 | QF | * | 4 | |
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| Win/loss | Clay | Hard | Carpet | Grass | Total |
| Since 1993 | 119/33 | 378/71 | 10/5 | 79/11 | 601/120 |
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