Some of the toll fee's on the French highways are hefty. I know that you can avoid them by taking the routes nationales, where some are almost like highways. I don't mind traveling a little bit longer to save money, but the 6 hours to drive 150 km I drove today to save 20 Euro was too much. Is there an easy way to determine when it is worth taking the secondary roads or when it is better to just pay the "péage".
Whether escaping the toll sections is a good idea or not really depends on the place.
So-called "routes nationales" (equivalent to the US Routes versus the Interstates) can be narrow winding roads crossing every village in some areas, and close to freeway quality with multiple separated lanes in others.
For example :
Most toll sections in France use a distance approach, where you pick up a ticket upon entering and pay on exit. Do not lose your ticket or the most expensive possible toll will be requested. The tip in the answers above apply, where entering and exiting multiple times can save you some cash.
A few sections, tipically shorter, use simpler, flat-toll barriers placed regularly, known as "tirelires" (money banks), with coin baskets. These are more found in the far southwest to the Spanish border, and around Nice. In my experience, it is better to pay the toll because, if you switch to the "nationale", you may wonder a good gridlock, especially during summer.
Also, other tips to save money include:
Got the following trick through other channels. You can save up to 20% by exiting a toll route multiple times. Apparently, the fares are not calculated based on the kilometers driven, but on specific trajectories.
Example: if you drive from Lille to Paris, you pay 15.60. If you exit and immediately re-enter the highway three times inbetween you pay 11 Euro.
Someone made a very handy map to calculate your saving: http://www.autoroute-eco.fr/autoroute.html. (French)
You can see the rates from A to B on the French motorways website (enter the departure and destination cities in the box on the right). You'll get a map and a breakdown of the route. Beware of the route shown near cities, it tends to show unnecessary detours.
The route breakdown tells you where the tolls are, but not where you would need to exit and reenter the motorway to avoid them. A good paper map would show you where the tolls are. So should a good GPS.
That same website also has a flash map with links to the website of the company that manages each motorway. These sites usually have more detailed information, but it isn't always easy to use as you'll sometimes need to know the name of the rural municipality where the motorway entrance or the toll is located, and many of these sites are in French only.
Some sites let you find an itinerary that avoids tolls, for example Via Michelin.
Remember that if you take the secondary roads, you'll be saving fuel by driving slower but you'll also be driving more kilometers, assuming that you could do most of the trip on a motorway. It's difficult to have a general rule as to what would cost less.