Michael Russell also warned that the UK will end up seeking to rejoin the Brussels bloc within 20 years if it pushes ahead with its planned departure in 2019.
The Scottish Government minister said that the Scottish Government was working on contingency plans to deal with the impact of a breakdown in talks, including independence.
Prime Minister Theresa May recently warned that "no deal is better than a bad deal" as she set out a tough stall going into talks with EU leaders.
"I think the chances of the UK not sticking with he negotiations are high," Mr Russell told Holyrood's European committee today.
"I don't think they are necessarily 50 per cent or 60 per cent but they're high. It is in our mind that we would have to be prepared in those circumstances.
"We have a range of scenarios that we look at regularly.
"You start probably with that issue and you work your way through ‘hard Brexit' with detriment to devolution, ‘hard Brexit' without detriment to devolution, ‘moderate Brexit' in which devolved powers are increased, through to independence, of course, which we believe is the offering that should be made.
"So we look at all of those and we have thought through some of the issues."
"But if there's going to be a collapse in negotiations it will probably happen sooner rather than later."
He added that the most likely issue to derail talks was the UK's departure bill with recent claims the EU will demand £100 billion.
Mr Russell said the EU leaders were "mystified and troubled" by the UK's decision to leave, but would not feel "hectored and pressured" by Theresa May because they have other issues on their agenda.
"There are bigger issues," he said.
"I actually think in 20 years’ time, if the UK does come out, in 20 years’ time the UK will be in the process of trying to be back in.
"And it will have lost 20 years influence and 20 years of progress and 20 years of prosperity."