The 30-year-old, who plays for Chinese club Changchun Yatai, last appeared for his country in a 3-0 defeat by England in a Euro 2012 qualifier in September 2011.
"A few days ago Lubo Penev called me to ask if I would agree to play under him," former CSKA Sofia and Anorthosis Famagusta midfielder Marquinhos told Bulgarian media.
"I immediately told him that I would be honoured to be part of the team again."
Botev Plovdiv striker Ivan Tsvetkov has also received his first call-up at the age of 33 despite not having Bulgarian citizenship.
"We have all the assurances that the documentation will be ready in time and he can take part in the friendly," Penev said.
Tsvetkov, who has scored seven goals in the domestic championship this season, has a Dutch passport after starting his career in the Netherlands in 1998.
Unbeaten Bulgaria have made a solid start to their 2014 World Cup qualifying campaign and are second in Group B with six points from four matches, four behind leaders Italy.
Ukraine are second from bottom in Group H with two points from three games, six behind leaders England who have played one more match.
- Sports & Recreation
- Ivan Tsvetkov
- Changchun Yatai
- Anorthosis Famagusta