The article reports on a new sampling method and the archaeological context of cave drawings, which include the oldest currently known graffiti in the Czech Republic. Between 2016 and 2020, samples with a small amount of charcoal were taken from drawings found in Kateřinská Cave (Catherine’s Cave) of the Moravian Karst in the Czech Republic. A new gentle method of sampling charcoal from the cave walls was developed for the purpose of radiocarbon (14C) dating cave drawings of unknown age, while preserving the contours of the drawings. 14C analysis has provided data from four periods of prehistory and history: from the Neolithic around 5000 BC, the turn of the Neolithic and Eneolithic around 4300 BC, the Hallstatt Period from 800–450 BC, and also from the Middle Ages (13th century). The radiocarbon dates of the graffiti correspond to the dates of the pottery finds from the entrance portal of Kateřinská Cave, thus validating the dates and the sampling method.