She took refuge in Bordeaux, where she was arrested and jailed as the former wife of an émigré aristocrat. She met Jean Lambert Tallien, the Commissary of the National Convention, who saved her from the guillotine, and became his mistress - through her influence, Thérésa Tallien obtained the release of many prisoners. She accompanied him when he was recalled to Paris, only to be imprisoned on Maximilien Robespierre's orders first in La Force prison, then in Carmes prison where she met Joséphine de Beauharnais. She married Tallien on 26 December 1794.
Thérésa became one of the leaders of the Parisian social life. Her salon was famous and she was one of the originators of the Neo-Grec women's fashion of the French Directory period. She was a very colorful figure; one story is that she was said to bathe in the juice of strawberries for their healing properties. She once arrived at the Tuileries Palace, the then chief residence of Napoleon Bonaparte, supported by a black page, with six sapphire rings in the feet, eight in the hands, two gold bracelets in the ankles, eighteen in the arms and a forehead band full of rubies. On another occasion she appeared at the Paris Opera wearing a white silk dress without sleeves and not wearing any underwear. Charles Maurice de Talleyrand commented: "Il n'est pas possible de s'exposer plus somptueusement!" ("It is not possible to exhibit oneself more sumptuously!").
Tallien's power waned and he and Thérésa divorced in 1802. After a brief flirtation with Napoleon, she moved first to the powerful Paul Barras; then to the millionaire speculator Gabriel-Julien Ouvrard; and finally, attempting to gain respectability, she married François-Joseph-Philippe de Riquet, Comte de Caraman, on 22 August 1805 - he had become the sixteenth Prince of Chimay after the death of his childless uncle in 1804. She spent the rest of her life first in Paris, then on the Chimay estates (now in Belgium). After the Battle of Waterloo in 1815, these became part of the United Kingdom of the Netherlands.
The couple invited musicians such as Daniel Auber, Rodolphe Kreutzer, Luigi Cherubini, Charles de Bériot and Maria Malibran to Paris and later to Chimay, where Thérésa held a little court. Cherubini composed his Mass in fa at their castle there.
Thérésa died in Chimay, where she was interred with François-Joseph de Riquet under the sacristy of the local church where a memorial stands to her memory. She bore ten children during her various liaisons, including Joseph de Riquet, first son of François-Joseph-Philippe, who became the seventeenth Prince of Chimay in 1843.