Large super-elasticity approaching its theoretically expected value was achieved in Ti-13.3Nb-4.6Mo alloy having an ultrafine-grained β-phase. In-situ synchrotron radiation X-ray diffraction analysis revealed that the dominant yielding mechanism changed from dislocation slip to martensitic transformation by decreasing the β-grain size down to sub-micrometer. Different grain size dependence of the critical stress to initiate dislocation slip and martensitic transformation, which was reflected by the transition of yielding behavior, was considered to be the main reason for the large super-elasticity in the ultrafine-grained specimen.