The nucleation behavior of α(TiCrSiO), a 1/1 Fibonacci crystal approximant phase, was investigated in alloys made near the stoichiometric composition. Containerless solidification studies were made with electromagnetic radio-frequency levitation and the 105-m NASA Drop Tube. The solidification microstructures indicate that the α–Ti hexagonal solid solution was the primary crystallizing phase in these alloys, growing dendritically. The α(TiCrSiO) phase nucleated in the remaining liquid. The competition between these two phases resulted from the high oxygen concentration needed to form α(TiCrSiO), which also stabilized the hexagonal-close-packed α–Ti phase.