The cementite spheroidization process is investigated in hypereutectoid steels with different chromium (Cr) contents. A spheroidized structure in high-carbon steel is usually obtained by a divorced eutectoid transformation (DET) reaction, which occurs during slow cooling of austenite with fine cementite particles. A bimodal distribution of spheroidized cementite particles is experimentally observed. It is shown that Cr addition allows one to obtain the spheroidized structure after austenitization at a higher temperature and a longer annealing time as compared with low-Cr steel. It is found that the DET reaction takes place at low undercoolings compared with the pearlitic reaction. The occurrence of the DET reaction also depends strongly on the spacing between cementite particles during the austenitization process, i.e., on austenitization temperature and time.