He fought for Henry IV at the battle of Coutras and also at Ivry, and was rewarded by elevation to the peerage, as Duke of Thouars, in 1595.
This new title, however, made La Trémoille lose more money than it earned him.
Thanks to her relations with the houses of Orange and Bouillon, Charlotte-Brabantine played an important part in the French Protestant diplomacy.
They had four children: Henry (1598–1674); Charlotte (1599–1664), who married James Stanley, Earl of Derby; Élisabeth (1601–1604) and Frédéric (1602–1642) comte de Laval.
In 1602, Charlotte-Brabantine dissuaded her husband from engaging in the conspiracy of Biron and encouraged him to lend allegiance to the king.