Zr_52.5Cu_17.9Ni_14.6Al₁₀Ti₅ bulk metallic glasses have been prepared by copper moulding. In order to obtain a fully amorphous sample, a careful control of the atmosphere conditions in the casting chamber was necessary. In particular, the presence of oxygen contamination promotes the nucleation of a fcc “big cube” phase, reducing glass formation. The crystallisation of bulk amorphous samples has been followed by DSC and values of about 4 kJ·mol⁻¹ have been obtained for the heat release at about 740 K. By high temperature DSC, a metastable-to-stable phase transformation has been evidenced at 938 K, which gives a heat evolution of 1.12 kJ·mol⁻¹. Melting and solidification of the alloy have been observed at 1070 K, giving an average value for the enthalpy change of about 8.2 kJ·mol⁻¹. The temperature dependence of the enthalpy difference between undercooled liquid and equilibrium crystal phases has been described on the basis of different models for the specific heat difference (ΔC_p) between the two phases. A best fitting of experimental data gives values of ΔC_p of about 21 J·mol⁻¹·K⁻¹ at the glass transition temperature (690 K), in good agreement with experimental values obtained from DSC measurements.