Maximum undercooling results for the icosahedral phase (i-phase), polytetrahedral C14 Laves phase, and solid solution phases are presented as a function of composition in Ti-Zr-Ni liquids. Containerless processing was achieved using the electrostatic levitation facility located at NASA/Marshall Space Flight Center. The maximum reduced undercooling decreases with increasing icosahedral short-range order in the ordered phase. The first synchrotron x-ray diffraction data from aerodynamically levitated liquids of Ti-Zr-Ni alloys suggest an icosahedral short-range order in the liquids, supporting Frank's hypothesis, correlating icosahedral order in the liquid with the nucleation barrier to the crystal phase. The strong negative heats of mixing between Ti/Zr and Ni and their relative atomic sizes likely favor the formation of this local icosahedral order.