The synthesis of alloy nanocatalysts with controllable sizes and shapes is a critical prerequisite for vapor–liquid–solid (VLS) growth of one-dimensional nanostructures. In this work, we comprehensively examined surface reactions between evaporated In atoms and a Bi thin film on a Si(111) surface at ambient temperature. InBi2 liquid nanodroplets nucleate and grow during initial vapor–solid (VS) reaction between the In vapor and surface Bi atoms, and the reaction proceeds until a saturation point is reached, following which InBi2 begins to catalyze subsequent VLS growth of various nanocrystals under persistent In-beam flux. The scaled size distribution of individual InBi2 nanodroplets could be explained adequately using the classical capillary nucleation theory, which suggests that the simultaneous homogeneous nucleation of InBi2 nanodroplets occurs during the vapor–solid (VS) reaction of In and Bi.