Orientation relationships (ORs) can form during solidification by a variety of mechanisms that are often difficult to distinguish after solidification. Here we study three ORs formed by the nucleation of Al3Ti on TiB2, and by the pushing and engulfment of TiB2 by growing Al3Ti facets in hyperperitectic Al-rich melts. The nucleation OR is identified by growing a relatively large TiB2 crystal, solidifying multiple small Al3Ti crystals on one (0001) facet of TiB2, and measuring the resulting OR by electron backscatter diffraction (EBSD). Pushing and engulfment ORs are investigated by statistical analysis of EBSD measurements, density functional theory (DFT) calculations of interface energies, and imaging of cross-sections of TiB2 particles being pushed and engulfed by Al3Ti facets. It is shown that the lowest energy OR is formed by nucleation as well as by pushing/engulfment. The higher energy ORs, formed by pushing and engulfment, correspond to local interfacial energy minima and can be explained by rotation of TiB2 particles on Al3Ti facets during pushing.