The article describes the correspondence legacy of Countess Ksawera Grocholska (1807–1872) found by the author in domestic and foreign archives. Grocholska belonged to the Polish landed gentry, and was a philanthropist, amateur artist, and owner of the Kniazhe estate in the Jampol county in Podolia. Grocholska’s extensive and dispersed letters were found in the collections of several archives and libraries throughout Europe. They are both her private letters and those written to the Russian authorities on issues related to issuing a passport for trips abroad, the marriage of the eldest daughter, Maria Czartoryska, née Grocholska, and the charity work carried out by Grocholska from the time of the Konarski conspiracy. These letters have been discussed in the literature for the first time as they have not been the research subject yet. In the essay, a problem-based system was adopted when describing the legacy, dividing the discovered letters into three basic categories: family and private letters, those concerning aid activities, and official writings. In each of these subgroups, chronological order has been adopted.