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|Perfect record: Serena Williams AFP/Greg Wood|
The 38-year-old icon teams with newly-crowned Australian Open champion Sofia Kenin and teenage star Coco Gauff as the US tackle Latvia in Everett, Washington.
In total, there are eight ties with the winners earning places in the new-look Fed Cup finals in Budapest from Apr 15-17 where 2019 champions France, runners-up Australia, hosts Hungary and wildcard Czech Republic will be waiting.
AFP Sports looks at three talking points ahead of this week's qualifiers:
Serena's senior service
-- It was back in 1999 that Serena Williams made her Fed Cup debut in a semi-final win over Italy.
Teammate Sofia Kenin was just eight months old while Coco Gauff was still almost five years away from being born.
Williams has a 100 per cent record in singles in the Fed Cup, winning 13 out of 13 rubbers.
However, despite her longevity, her relationship with the tournament has been very much on-off, playing only in 1999, 2003, 2007, 2012, 2013, 2015 and 2018.
Kenin, now the top-ranked US player at seven in the world after her stunning Grand Slam breakthrough in Melbourne, has a Fed Cup singles record of 1-3 while 15-year-old Gauff has yet to make her debut.
Osaka eyes Japan breakthrough
-- Two-time Grand Slam champion Naomi Osaka is making her first Fed Cup appearance since helping Japan defeat Great Britain in the 2018 World Group II play-offs.
The world number 10 has won five out of six singles ties she has contested since her 2017 debut.
However, Japan, whose best Fed Cup run was a semi-final spot in 1996, have a tough task this weekend, facing Spain in La Manga.
Japan lost to the Spanish in a World Group II tie last year when Osaka opted to rest.
"I am really happy to be back," said Osaka at Thursday's draw which pitted her against world number 78 Sara Sorribes Tormo in Friday's opener.
"It would be very special to reach the finals, everyone has worked hard to get this far.
"We lost last year but I hope I can make the difference. That's why I am here. Even if it's on clay and everyone knows I am a hardcourt player.
"I'm trying to learn it."
Clay courts play easily into the comfort zone of a Spain team led by Carla Suarez Navarro, her nation's top player in the absence of Australian Open runner-up Garbine Muguruza.
It will be an emotional week for 31-year-old Suarez Navarro as the world number 55 is in her final season as a professional, 12 years after her Fed Cup bow.
Spain are five-time champions, behind the USA (18), Czech Republic (10) and Australia (seven) on the all-time list.
Olympics are Fed Cup factor
-- Places at the Tokyo Olympics are also up for grabs on Friday and Saturday in the eight ties.
Under Fed Cup rules, players are required to be part of a nominated team on at least three occasions in a four-year Olympic cycle.
That excludes players who have represented their nation 20 or more times in their careers, who must be nominated on at least two occasions in the Olympic cycle.
Crucially for this week, all players must be nominated at least once in the 2019-20 cycle.
Serena was 2012 Olympic champion in London while Rio 2016 gold medallist Monica Puig comfortably fulfils the basic qualifying criteria despite a current lowly world ranking of 83.