Assuming the car has been in hot sunlight but the outdoor temperature is tolerable, the most fuel efficient way is to ventilate without any AC, just by using fan at max speed, blend door at coldest possible position and keeping the windows open. Once the temperature of air inside the car becomes tolerable, then turn on the AC, set the fan to low speed, set blend door to coldest possible position and close windows. If you hit high speeds (80 km/h and above) before the temperature of air inside the car becomes tolerable, then close windows when hitting that speed (earlier than you would otherwise close them), turn on the AC and set fan to a speed that cools the car interior at a comfortable pace. If it becomes too cold, you may slightly increase the blend door to warmer, but the preference is this: first reduce fan speed, and only then if it doesn't help set blend door to warmer position.
The reason for these is that the performance of keeping windows open is best with largest temperature difference (outdoor air comfortable, air inside car very hot). The fuel efficiency of keeping windows open exceeds that of air conditioning if you are traveling at slow speeds. Also if you cool down air and then use blend door to mix in air heated by engine, that's just wasting energy. Therefore the blend door should be always at coldest possible position.
In theory, if the outdoor air isn't very hot, and you drive the entire trip at slow speeds, in that case you could of course keep the windows open during the entire journey. But the savings would be small, and it's hard to control the temperature precisely, so even minor priority on comfort dictates using the AC instead of keeping windows open.
In automatic climate control systems, the automatic mode works as follows:
- AC is on
- Initially, fan is at very high speed, blend door at coldest position
- Then, when temperature drops to near the setpoint, fan will be at low speed, blend door at coldest position (but if it nevertheless becomes too cold, then the blend door will be moved to mix some air heated by the engine)
This is the best plan if you're not going to open the windows at all. However, it wastes a bit of fuel compared to initially rapidly ventilating with all windows open when driving at low speed, and only after that using the automatic mode of the climate control system.
If outdoor air is very hot, then windows should never be opened. Instead, just use the AC.
Most recent cars have an AC compressor that has variable power. Thus, to save on the energy, you want to reduce the load on it as much as you can. You don't do that by cooling down lots of air and then mixing hot engine air using the blend door -- instead, you move little air with blend door in coldest position.