The Gothic brick Eglise des Jacobins, parvis des Jacobins (tel. 05-61-22-21-92), in Old Toulouse, is west of place du Capitole along rue Lakanal. The church and the restored convent, daring in its architecture and use of "palm tree"-shaped vaults, form the largest extant monastery complex in France. It's open daily 9am to 7pm. Admission to most of the complex is free, but a visit to the cloisters costs 3€ ($3.90).
Small, charming, and dating mostly from the 18th century, the Basilique Notre-Dame La Daurade, 1 place de la Daurade (tel. 05-61-21-38-32), gets its name from the gilding that covers its partially baroque exterior. Its prize possession is a statue of the Black Virgin, about 1m (3 1/4 ft.) tall, to which some locals attribute quasi-mystical powers. The one you'll see today was crafted in 1807 as a replacement for a much older statue that was burned during the French Revolution. Admission is free, and the Basilique Notre-Dame is open daily 8:30am to 6:30pm.
In civic architecture, Le Capitole, place du Capitole (tel. 05-61-22-34-12), is an outstanding achievement and one of the most potent symbols of Toulouse. Built in a baroque style in 1753, it houses the Hôtel de Ville (city hall) as well as the Théâtre National du Capitole (tel. 05-61-22-31-31), which presents concerts, ballets, and operas. Renovated in 1996, it's outfitted in an Italian-inspired 18th-century style with shades of scarlet and gold. Admission, which usually includes a view of the theater, is free. The Capitole complex is open Monday to Saturday 9am to 5pm, and until 7pm during holidays.
After sightseeing, head for place Wilson, a showcase 19th-century square (actually an oval) lined with fashionable cafes.