Amorphization and crystallization behaviors of Ti_50Cu_50Ni_20Al_10 powders during high-energy ball milling and subsequent heat treatment were studied. Full amorphization obtained after milling for 30 h was confirmed by X-ray diffraction and transmission electron microscope. The morphology of powders prepared using different milling times was observed by field-emission scanning electron microscope. The powders developed a fine, layered, homogeneous structure with prolonged milling. The crystallization behavior showed that the glass transition, T_g, onset crystallization, T_x, and super cooled liquid range DeltaT=T_x-T_g were 691,771 and 80 K, respectively. The isothermal transformation kinetics was analyzed by the John-Mehn-Avrami equation. The Avrami exponent was close to 2.5, which corresponds to the transformation process with a diffusion-controlled type at nearly constant nucleation rate. The activation energy of crystallization for the alloy in the isothermal annealing process calculated using an Arrhenius plot was 345 kJ/mol.