Thermal analysis allows for determination of temperature specific for the beginning and the end of phase transitions occurring in studied samples. In this paper results obtained from DTA (Differential Thermal Analysis) of alloys of chemical composition referring to nickel-rich part of Ni-Al-Cr system, specifically from section Ni75Al25÷Ni65Cr35 are presented. Those alloys are based on intermetallic phase Ni3Al. Referring to measurements obtained during heating and cooling, characteristic peaks related to occurrence of phase transition of order-disorder type were noted as well as melting and solidification temperature of alloys was determined. Results of thermal analysis DTA of studied range were compared with results obtained for section Ni75Al25÷Ni75Cr25 and Ni75Al25÷Ni87Cr13, additionally results of measurements performed on high-temperature solution calorimeter were collated. Both methods presented good compatibility.