Mike Russell says the party has a “triple mandate” to take steps to protect Scotland’s place in Europe, which would justify blocking the UK Government’s plans to trigger Article 50.
His comments come as UK Health Secretary Jeremy Hunt insisted MPs will fall into line when it comes to backing the process.
Speaking on BBC Scotland’s Sunday Politics Scotland programme, Mr Russell said calls from other parties for the UK to remain in the single market after Brexit - a key Scottish Government demand - “bode well” for the SNP working with others.
“It’s good to see a view emerging that at the very least membership of the single market must be paramount in our position,” he said.
But when asked if there were any circumstances in which the SNP’s 54 MPs would vote to start the exit process, he said: “I can’t imagine what those would be. “We don’t know the UK position, so it is possible there could be a complete capitulation on all the positions they have held up to now.
“I think it would be very difficult to imagine what that would be.”
The SNP’s “triple mandate” includes its manifesto commitments at the 2016 Scottish election, Scotland’s majority vote in favour of Remain, and Scottish Parliament support for efforts to protect Scotland’s place in Europe.
Mr Russell said the Scottish Government is still deciding whether to become an active participant in the appeal against the court ruling that Parliament must vote on whether Article 50 can be triggered.
The Welsh Government has already announced it is to apply to have a voice.
“Now we have to consider the benefits of making sure the Scottish Government is involved in this case,” he said.
Mr Russell said it was a “possibility” the court could be asked to rule that legislative consent for Brexit from Holyrood is necessary. He said: “The Welsh First Minister has made it very clear on many occasions, and we support him on this, that there should be a role for all the parliaments in these islands.
“They can’t just be swept to one side. Theresa May’s intention just to bulldoze ahead with a plan which she doesn’t actually even appear to have is very foolish indeed.”
He added: “From the very beginning we have been saying it is essential that we are involved in this process and deeply involved.”
Mr Russell continued: “It would be completely unchartered if the Scottish Parliament refused legislative consent and the UK Government said well it doesn’t matter we’re going to do it anyway.
“The people of Scotland would draw their own conclusions in a situation in which there was no partnership, no agreement between the two nations, but a contempt for the legislative process and the view of Scotland.”
“It would have huge political force.”