Graphite has been widely used as a negative electrode material in lithium-ion batteries, and recently it has attracted attention for its use in potassium-ion batteries. In this study, the first in situ X-ray diffraction characterisation of a K/graphite electrochemical cell is performed. Various graphite intercalation compounds are found, including the stage three KC36 and stage one KC8 compounds, along with the disappearance of the graphite during the potassiation process. These results show new insights on the non-equilibrium states of potassium-ion intercalation into graphite in K/graphite electrochemical cells.