The phase transition of two liquid crystalline materials, namely cholesteryl palmitate and cholesteryl decanoate and their mixtures (by weight)are studied using dielectric, Electron paramagnetic resonance (EPR) and differential thermal analysis (DTA) techniques. From the dielectric measurements, the phase transition temperatures were determined from the discontinuities in the curve between dielectric constant and temperatures for all the samples investigated. Further, since mixing of two liquid crystals modifies the transition of phases, the measurements were carried out on the mixtures of the two liquid crystals. Order parameter for each sample was calculated at varying temperatures by measuring the hyperfine splitting of three line EPR spectrums. The discontinuities in the curve between order parameter and the temperature again indicated the phase transition of the liquid crystals and their mixtures. A DTA study on these samples was also carried out in order to probe further their transitional behaviour. The DTA records of both the liquid crystals and their mixtures support the transition behaviour observed from the dielectric and EPR measurements.