Australia, Argentina and Slovakia needed only the first of Sunday's reverse singles to advance, while Italy secured victory in the second reverse singles in the Fed Cup play-offs.
Australia, seven-time champions, completed a 5-0 sweep of Austria with singles wins by Nicole Pratt and Alicia Molik and a doubles victory by Evie Dominikovic and Rachel McQuillan in Adelaide.
Argentina saw off Japan when Maria Emilia Salerni, the reigning world junior champion, defeated Yuka Yoshida 7-5 6-0 in the first singles match of the day and took the series, 4-1 in Tokyo.
Slovakia defeated Hungary when Henrieta Nagyova rallied to beat Rita Kuti Kis 2-6 7-6 (10-8) 7-5, in singles and went on to win the series 4-1 in Bratislava.
Giula Casoni and Adriana Serra-Zanetti won the first two reverse singles matches today to clinch the series for Italy against Croatia, who closed out with a doubles victory.
Casoni defeated Matea Mezak 6-2 6-4 and Serra-Zanetti beat Jelena Kostanic 6-1 7-6 (7-5).
The Fed Cup has undergone a format change for the third straight year, with the defending champion United States on the sidelines until the finals.
In past years, the international women's tennis competition had been contested under a single-elimination format involving eight nations.
Last year, the event went through a significant change as three round-robin groups were set up so that the winner of each group would advance to the semi-finals, along with the defending champion acting as the host nation.
The 2001 version of Fed Cup will consist of two play-off rounds, each involving eight nations. The four winners from this weekend's ties will go on to face another four nations in the second play-off round from July 22.
Those second-round winners will meet four other nations, including the US, in a round-robin format in November to determine the champion.
Italy will face France in the second round of play-offs in July, Argentina meets Germany, Slovakia will take on Hungary and Australia faces Switzerland.
The US, Spain, Belgium and the Czech Republic, all semifinalists last year, have already qualified for the finals.