Uefa president Michel Platini is set to revisit sites in the Ukraine after being dismayed by lack of progress in terms of stadiums and infrastructure earlier this year.
Scotland failed in a joint bid with Ireland for Euro 2008, but are confident that they can bolster currently suitable venues Hampden Park, Ibrox, Celtic Park and Murrayfield in time for the 2012 showpiece.
SFA chief executive Gordon Smith told BBC Scotland: "We have made it clear that we'd like to be considered if it's not going ahead in Ukraine and Poland.
"With the event likely to expand after 2012 it would be our last chance."
Smith revealed that he has already spoken to Uefa president Michel Platini about using Scotland as a host nation, adding: "I asked if the size of the competition was increasing from 16 teams.
"And, given that it probably would after 2012, we would not be able to stage a European Championship if that was the case.
"But he (Platini) said there might be an opportunity, you never know.
"There is an inspection on Ukraine and Poland's facilities in June or July and if they don't match up they may have to take the tournament elsewhere.
"I said was that we'd like to be considered if that situation arose. We haven't been told we are on standby or anything like that."
The Ukrainian FA admits that there are concerns, but insists that Uefa have made no mention of stripping them of their hosting status.
FA member Igor Miroshnychenko said: "I have heard the story about the possibility of the championships being taken off us.
"I spoke with Uefa on Wednesday and they told me that they have no plans at the moment to move elsewhere, but it's not a good situation here at the moment.
"We have no main stadium and there are problems with the roads; it's not a good situation politically.
"People here feel there are too many problems to host this tournament. Can we host it? I really don't know."