Languedoc - What about City of Toulouse?

Toulouse is the 4th city of France (it is called "the pink city" because of the stones with which the buildings and houses are built. There are a lot of things to do and see in Toulouse, you could stay there one night or two,
It is also the European capital of aerospace and aeronautics with the Airbus factories and all other activities related to space and aviation.

Toulouse can be a "hub" to visit Albi which is 45 minutes away.

https://www.toulouse-visit.com/

But if you don't care about aeronautics, pink houses, prefer to stay in a smaller town and then continue to Languedoc you can also go directly to Albi without going through Toulouse

I even know an interesting route from Sarlat to Albi which passes through several "most beautiful villages in France" without going through Toulouse (I live in this region) and which does not take much longer than by the A20 motorway (except that on this route there are some nice places to stop).
Since you'll have a car, and if you're ever interested...

From Albi you could also go to Carcassonne avoiding the highways.

Languedoc is big. It goes from the Spanish border to Nimes and there are a lot of things to see, eat and drink. Lots of regional parks. It's hard to recommend a particular place. You can spend a week there and only see a quarter of it.

In any case go to Montpellier, it is the capital of Languedoc

I found Toulouse very attractive and would choose it over the smaller towns for myself. It just has more to see. Though I did enjoy a day trip to Albi in 2017, it was shockingly quiet in the afternoon (on an oppressively hot summer day, I admit), and I wonder what it would be like to spend multiple nights there...

However, it sounds like you'll be keeping the car while in Languedoc, and I have no idea whether Toulouse would present parking or navigational challenges.

There are lots of interesting towns in that region. You could mosey along for quite some time there. The Cathar sites sound intriguing, but it wasn't practical for me to visit them since I had no car.

Three nights in the Dordogne sounds light to me.

We visited Toulouse and loved it. Great town for walking. Good food, shopping, riverside parks, vibrant university scene. I wouldn't want a car. We trained up to Albi, that was great, with a car you could visit Cordes-sur-Ciel.

Toulouse is a good place to stay. You can take a lot of day trips to visit all the places mentioned. Cords-sur-ciel is very much worth visiting. I also agree that three nights is a bit short for the Dordogne. Meanwhile, I'd find five nights too long for the Loire but some people like the chateau more than the caves and vice versa.

JoLui is right that there are sites and sights everywhere in the Languedoc, most not in RS books because his cover mainly where his tours go. But they are in the Green Michelin Guidebooks and many others.

As for which is the capital--LOL--it's a constant tug-a-war between Toulouse and Montpellier but that just makes each city try harder to be number 1. Toulouse may be #4 in France, but Montpellier has been the fastest growing for the past twenty-five years, while still retaining its historic center.

I mentioned Toulouse as the 4th city of France only in terms of population.
I lived a few years in Toulouse but I'm far from being a fanatic.

To choose, like many others, I prefer Montpellier where I also spent time.

As for where the capital is... I pass.

Or I choose Perpignan, whose train station is the center of the universe. :))