The rapid solidification of ternary NiAl-Mo eutectic alloy is investigated by using melt-spinning technique, and the conventional casting is also carried out for a comparison study. The phase constitutions of the alloy samples obtained from different experiments each include both B2-NiAl intermetallic and bcc-Mo solid solution, which are both presented in the 〈110〉priority growth direction. The growth orientation relationship of the coupled two eutectic phases are obtained to be (110)NiAl//(110)Mo. The cast alloy is composed mainly of two regular eutectic phases in structure and exhibits daisy-like eutectic cells. However, the melt-spinning ribbons show the microstructures of the columnar grain near the roller surface zone and the equiaxed grain near the air zone. With the wheel speed increasing from 10 m/s to 50 m/s, the cooling rate of the alloy ribbons increases from 1.01×107 K/s to 2.46×107 K/s, while the thickness of alloy ribbons decreases from 49.4 μm to 22 μm. Meanwhile, the volume fraction of columnar grain zone increases gradually, and the grains are refined obviously. The cooling rate in the melt-spinning experiment for alloy ribbon is obviously higher than that in the conventional casting test, which leads to a significant difference in solidification microstructure between two techniques.