This paper investigates the potential of the Modulated Differential Scanning Calorimetry (MDSCT(TM)) technique in the thermal characterisation of various amorphous materials. Inorganic glasses, composites and glass-polymer mixed materials have been investigated in order to separate the glass transition from irreversible phenomena, such as cold crystallisation or residual cure. This new technique requires some additional experimental parameters to be set, whose role in affecting thermal signals is also briefly discussed.