New Davis Cup captain John Lloyd has selected Jamie Baker and Alan Mackin in his first Great Britain team.
Baker has been a hitting partner in Davis Cup before
Great Britain play Ukraine in a Euro-Africa Group One relegation tie in Odessa on 22-24 September.
The visitors are likely to rely heavily on British number one Andy Murray and veteran Greg Rusedski.
Baker, 20, will be playing his first tie, while fellow Glaswegian Alan Mackin, 25, has a 1-3 record in Davis Cup singles rubbers.
The LTA have confirmed that is the first time that three Scots have been included in a GB Davis Cup team - and, with Rusedski being Canadian-born, the first time no Englishman has been named.
Lloyd, who succeeded Jeremy Bates as captain after GB's defeat to Israel in July, said: "I have selected a team that has plenty of Davis Cup experience, and who are comfortable playing on clay.
"Andy has been in phenomenal form recently and will come into this tie full of confidence.
"I am very pleased to name Greg in the team, his Davis Cup record and experience will be invaluable for all members of the squad.
Peter Lundgren has a fantastic tennis pedigree and the players are looking forward to working with him
"I believe all members of the squad have the ability and temperament to step up and deliver their very best performances during this difficult tie.
"We are all fully aware of the importance of this play-off and are very much looking forward to getting our preparations underway."
Those preparations include a five-day training camp in Vienna, Austria before arriving in Odessa.
Lloyd will be assisted by Peter Lundgren, former coach of world number one Roger Federer, who was appointed on Sunday.
The captain said: "He has a fantastic tennis pedigree and I know that all the players are looking forward to working with him.
"We will be training extremely hard in the run-up to this tie to ensure that we are fully prepared and I am confident this will be reflected in a victory."
Great Britain have played Ukraine twice before, winning on both occasions.