Kim Clijsters and Justine Henin-Hardenne earned Belgium a semi-final showdown with the U.S. after propelling their country to a 5-0 rout of holders Slovakia in the Fed Cup on Sunday.
Despite the absence of their top four players, a depleted American team whitewashed Italy 5-0.
An impressive France trounced five-times champions Spain 4-1 to set up a last-four date with Russia, who whitewashed Slovenia 5-0.
Slovakia limped out of the tournament after world number two Clijsters thrashed Janette Husarova 6-0, 6-1 in 40 minutes in Charleroi.
Henin offered little respite to the visitors, demolishing Eva Fislova 6-2, 6-1 while Els Callens and Caroline Maes completed the drubbing.
"We achieved our goal and we won," said French Open champion Henin.
"We were favourites on paper but it doesn't always go according to the script.
"Now that we've qualified for the semis, we want to go further."
Missing the services of their leading player, world number nine Daniela Hantuchova, Slovakia relinquished the title they won for the first time in 2002 without winning a set.
It is the second year running that the title holders have been beaten in the quarter-finals. Twelve months ago, 2001 winners Belgium suffered a similar fate at the hands of Italy after Clijsters and Henin ruled themselves out of the tie to concentrate on their individual careers.
While Slovakia were always facing a tall order against a team featuring two of the world's top three players, Hantuchova's decision to skip the trip effectively sealed their fate before the contest had started.
BATTLING RUBIN
Handed the task of spearheading the U.S. campaign in Washington, world number eight Chanda Rubin ensured the 17-times champions a spot in the semi-finals when a battling 5-7, 6-4, 6-0 triumph over Francesca Schiavone gave her side a winning 3-0 margin.
While world number one Serena Williams chose to sit out the clash, her sister Venus pulled out with an abdominal strain. Lindsay Davenport and Jennifer Capriati were not considered after falling out of favour with captain Billie Jean King.
When asked by reporters if she had decided who would play against Belgium, King replied: "No, but I'm going to wait until it gets closer to the time and then I'll go by the rankings before asking (the players)."
Amelie Mauresmo beat Magui Serna 7-5, 6-2 to give 1997 winners France a winning lead over Spain before Stephanie Cohen-Aloro extended the margin to 4-0.
Serna battled to keep Spain alive in the tie after two singles defeats on Saturday and gained an early break against Mauresmo.
The powerful Frenchwoman hit back with two breaks of serve to clinch the first set and completed victory in one hour 37 minutes.
"I was slightly concerned at the start of the third match but Amelie played very well after a bad start," French captain Guy Forget said.
"It's always nice to be 2-0 up after the first day and from then on the girls saw that the win was possible."
Elena Bovina stepped in for Russian number one Anastasia Myskina to overcome Slovenia's Katarina Srebotnik 7-6, 6-2 in the day's opening rubber in Portoroz, giving the Russians an unbeatable 3-0 lead.
With Slovenia playing in the World Group for the first time Srebotnik had engineered her country's opening round win over Argentina.
But the world number 35, who was beaten by Elena Dementieva on Saturday, was unable to repeat the feat against the talented Russians.
Srebotnik surrendered after an hour and 40 minutes.
The semi-finals and final will be played at one venue during the week starting November 17.