The 18-year-old Dane earlier cruised through with a 6-2 6-2 drubbing of Spanish 20th seed Anabel Medina Garrigues.
On Saturday, world number nine Vera Zvonareva beat Medina Garrigues 6-3 6-4 in the opening rubber of the tie.
He then had to watch Ivanovic lose a two-hour 38 minute tussle with Garrigues before they were second best in the doubles.
However, her older sister Venus was forced to withdraw ahead of her match against Spain's Anabel Medina Garrigues due to a back injury.
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Once again the mixed doubles proved the decider and Medina Garrigues and Verdasco paired to see off Johansson and Tsonga (FRA) 6-3 6-3.
However Spanish tenth seed Anabel Medina Garrigues became the first high-profile casualty of the tournament, losing 7-5 6-3 to 98th ranked Australian Anastasia Rodionova.
In the other half of the draw, second seed Svetlana Kuznetsova received a walkover when unseeded Spaniard Anabel Medina Garrigues pulled out with a back injury.
Meanwhile, Marion Bartoli of France beat Anabel Medina Garrigues of Spain 6-2 6-1 and seventh-seeded Marlene Weingartner of Germany eased past Aranxta Parra of Spain 6-2 7-5.
Kirsten Flipkens beat Anabel Medina Garrigues 7-6 (7-5) 1-6 6-2 in an opening rubber that lasted more than two hours in the crushing heat of south Spain.
Jo-Wilfried Tsonga put France ahead as he beat Fernando Verdasco 7-5 6-3, but Anabel Medina Garrigues leveled it for Spain with a 6-3 6-2 win over Mathilde Johansson.
But Williams has also hit a bump or two along the way, including a tight three-setter against Anabel Medina Garrigues in Madrid (Garrigues won the second set at love).
Safarova didn't leave Charleston empty-handed, however, securing her first WTA doubles title alongside Russia's Anastasia Pavlyuchenkova as they beat Spaniards Anabel Medina Garrigues and Yaroslava Shvedova 5-7 6-4 10-6.
On Sunday, Kuznetsova had to dig in for her win as world number 29 Medina Garrigues tried to salvage some home pride on clay at Club de Campo Villa de Madrid.
But 25th seed Anabel Medina Garrigues of Spain crashed out 1-6 6-4 6-0 to South African Chanelle Scheepers, while two-time grand slam champion Svetlana Kuznetsova, seeded 26th, lost 1-6 7-6 7-6 to Czech Iveta Benesova.
Spanish 26th seed Anabel Medina Garrigues went through 6-3 6-3 against Czech Eva Birnerova, while Slovakian 20th seed Daniela Hantuchova recovering from dropping the opening set to Uzbekistan-born American Varvara Lepchenko to win 4-6 6-3 6-2.
They also won the mixed doubles to complete a third successive victory in Group A and set up a clash with Spain's Fernando Verdasco and Anabel Medina Garrigues, who won all three of their Group B matches.
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