Europe/Africa Group I takes place in Tallinn and involves 14 teams divided into groups, with Britain facing Turkey, Latvia and Portugal in Group C.
The four winners will progress to promotion play-offs on Saturday, with two nations qualifying at the end of the week for World Group II play-offs in April.
World number one Andy Murray inspired Great Britain to Davis Cup victory in 2015 – but his mother, Judy Murray, quit as Fed Cup captain last year, frustrated at the competition’s format and Britain’s failure to progress.
“The format doesn’t lend itself to anything – but it is what it is and we have to accept that,” added Keothavong, who played in 39 ties for Great Britain.
“There’s only eight teams in the Fed Cup World Group whereas the Davis Cup has 16 so, with the format, it will take us a few years to get there.
“But we can certainly put women’s tennis on the map in this country.”
Latvia’s world number 35 Jelena Ostapenko is the highest-ranked opponent Britain will face in the round-robin stage, while Croatia – seeded to meet the Group C winners in Saturday’s play-off – have selected 37th-ranked Ana Konjuh and 84th-ranked Donna Vekic.
Should Britain’s women make it through to the World Group II play-offs in April, it could see them given a home Fed Cup tie for the first time since 1993.
They fell at the same stage in 2012 and 2013 – away ties in Sweden and Argentina – under the captaincy of Murray.