Appearing as a Unicef goodwill ambassador at a Commonwealth Games briefing in Glasgow, the former James Bond star was asked if he had any thoughts on September's referendum.
But Sir Roger kept his counsel.
"If I did, I would not make any comment about it because I'm here as a Unicef goodwill ambassador," he said.
"Unicef, although it's a branch of the United Nations, is not financially supported by the UN - it's entirely by voluntary contributions.
"One of the stipulations is that we do not express any opinion that might be political because we want to be heard and seen everywhere in the world."
After Daniel Craig's memorable appearance in accompanying the Queen to the opening ceremony of the London Olympics via parachute in a spoof short film two years ago, Sir Roger was asked if he would be seeing any other Bond actors in Glasgow and how he would be arriving at tomorrow's opening ceremony.
"Do I anticipate meeting any other James Bonds while I'm here? I haven't heard from Sean (Connery)," he said.
"As for making an entrance, there are no plans for that. I'm allergic to helicopters."
Sir Roger was appearing as part of a panel that included Glasgow 2014 chief executive David Grevemberg, Unicef chief operating officer Jon Sparkes, Unicef UK ambassador and former film producer Lord Puttnam, and Unicef youth ambassador for Malawi Monica Dzonzi.
The 86-year-old English actor said: "In the 24 years I've been with Unicef, it's been a happy experience.
"When I joined I was given pamphlets with stats I found boring to look at. But one statistic stands out in my mind, which was that 40,000 children die every day from preventable causes around the world.
"I'm glad to say that figure has been drastically reduced to 20,000, but even one is too many.
"Twenty thousand is a horrendous figure - to imagine that it happens every day."
Sir Roger recalled experiences of visits to Africa, saying that children would always give Unicef missions a warm welcome before the plight of locals became clear.
"The parents were hidden away or they were already dead from HIV/Aids," he said.
"I remember one lady looking at me with vast, rheumy eyes, and she said 'When we were young we thought we were human beings; now we're not even like animals. We send the children into the scrub, into the woods, to bring back roots and we chew them. If it doesn't kill us, we let the children eat them'.
"It was an awful, awful story to hear."
He added: "I'm proud to be a part of this organisation. I thank Scotland for having this partnership of the Commonwealth Games and Unicef."
Tomorrow's opening ceremony will see spectators at Celtic Park and millions watching on television afforded the opportunity to donate by text message to Unicef.
The suggestion of the ceremony becoming a "telethon" was played down by David Sparkes, chief operating officer of Unicef.
He said: "No, it is an opening ceremony. We're an important part. Our values and the Games' values are very similar.
"There will be a moment where everybody involved - the athletes, the audience in the stadium, the people watching on TV - will have the opportunity to support us by text or through online donations, but it's not going to be a traditional telethon."
Lord Puttnam, who as producer of the Oscar-winning Chariots Of Fire chose Scotland's St Andrews beaches for scenes that bookend the film, believes the charity of which he is a UK ambassador can see "something remarkable happen" in Glasgow.
"I think tomorrow night will prove that something is possible which will be picked up and used at every major sporting event - I cannot imagine the next football World Cup not finding means of allowing people to participate in giving and contributing to something that they themselves, Fifa, are promoting," Lord Puttnam said.
"Glasgow has this history of being the first to take on causes and the first to advance the notion of humanity being applied right across the board. It was a natural city."