Homogeneous crystals of Bi‐Sb solid solutions are difficult to grow, but are important for the basic understanding of the electron transport properties and band structure of these materials. The problems arise from (1) the low melting temperature (approximately 300°C) which makes it difficult to achieve a large thermal gradient at the crystal growing interface; (2) the small liquid diffusion coefficient which was estimated to be between 2 and 3×10−5cm2/sec at 300°C; and (3) a segregation coefficient so large (5–10) as to favor growth of undesirable cellular substructure. Under existing theories of crystal growth, the conditions necessary for producing crystals with Sb compositions from 5% to 14% free of macro‐ and micro‐inhomogeneity are described. A zone‐melting technique was used to grow the crystals with temperature gradients in the molten zone about 60°C/cm and growth rates between 1.6 and 0.4 mm/h. The degree of homogeneity was determined by etching studies, chemical analysis, and electron beam microprobing. Preliminary electrical measurements show considerable difference from previous measurements, particularly for the higher Sb contents.