Basing on the results of di erential scanning calorimetry and transmitted light intensity methods and texture observations in the temperature range from −50 ◦C to 90 ◦C phase diagram of 1-[3- uoro-4-(1-methylheptyloxycarbonyl)phenyl]-2-[4′ -(2,2,3,3,4,4,4-hepta uorobutoxybutoxy)biphenyl-4-yl]ethane was established. Monotropic system of thermodynamic phases was found. On cooling the isotropic phase transforms at 85 ◦C to ferroelectric SmC∗ phase and further two liquid crystalline phases, antiferroelectric SmC∗ A and SmI, and a metastable crystal Cr2 reveal. During heating exothermic anomaly in the wide temperature range was observed and ascribed to evolution of Cr2 to the stable crystal Cr1. On further heating both SmC∗ A and SmC∗ phases were observed. Thermodynamic parameters were calculated for all phase transitions. During rapid cooling (10 K/min) vitri cation of metastable Cr2 crystal at T_g = −115 ◦C was registered.