Peter Campsie, from Montrose, was killed in an attempted carjacking in the Brazilian city as he headed home to his family after a business meeting last Wednesday.
Mr Campsie, an operations manager for Diamond Offshore Drilling International, lived with his wife Janaina and 10-year-old daughter Joy in the city of Macae, north of Rio.
Mr Salmond said: "This is an extremely distressing incident and my thoughts and condolences are with the family during this very difficult time."
Mr Campsie's family said the 48-year-old, who had worked in Brazil for 16 years, was "a man who loved life", who brought joy and laughter to all around him.
In a statement, the family said he was "a loyal friend and father, brother and son who cared deeply about making sure everyone got the best out of their lives".
It is understood the father-of-three was shot twice and died at the scene of the attack on Wednesday.
The keen golfer still has family, including two sons and a brother and sister, in the north east of Scotland.
A spokeswoman for the Foreign and Commonwealth Office said: "We were made aware of the death of a British national in Brazil on 2 April.
"We stand ready to provide consular assistance to the family at this difficult time."