III/V semiconductor alloys have been extensively studied because of their usefulness for electronic and photonic devices. Nevertheless, the search for new alloys for specific applications continues. Often, thermodynamic factors restrict the compositional range accessible by epitaxial growth processes, particularly when the size difference between atoms mixing on a particular sublattice is large. This causes solid phase immiscibility, leading to important effects on the epitaxial growth, the resultant alloy properties, and, consequently, device performance. Stringent thermodynamic limits exist for a number of alloys being considered for advanced LED, laser, and solar cell applications where the atomic sizes are very dissimilar, such as GaInN, GaAsN and GaAsBi. This paper will review the basic thermodynamics of the epitaxial growth processes and mixing in semiconductor alloys, as well as the causes and consequences of the resultant complex microstructures.