It's about 200 miles, mostly on two-lane country highway, and would take around 4.5 hours plus stops. It would be no more difficult than any 200-mile drive along country roads.
You can get driving directions and rather optimistic times from www.viamichelin.com
Although I haven't done the continuous trip I've driven to Andorra on separate occasions from near both these cities, and it is not a difficult drive at all.
Luckily you don't need to go into central Barcelona from the airport, you can miss the worst of the traffic. If you don't like heights or roads with deep drops off the side then beware of the decent from Andorra into France.
I would have put the drive time at about 5 hrs and the distance of 200 miles (320km) seems short. Checked Google maps - 400km. After many thousands of km touring I have found google more accurate, and nore flexible. But Michelin gives the cost of your route, and is good for sightseeing.
I also prefer Google maps... here's a link to a proposed route:
Google puts it at 325 Km and 4 hours 13 minutes. I'd give it more time than that as their estimate works out to nearly 80 kph... if you make any stops or get behind a truck or bus you'll be slowed down.
I particularly enjoyed an afternoon in Foix. There are many other interesting places such as Mirepoix and Mont Segur on the French side of the mountains.
Last summer we drove from Perpignan to Andorra to Carcassonne. The roads are small and narrow and twisty and I enjoyed every second behind the wheel!
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