Phase separation in III–V semiconductors has led to a unique method for fabricating quantum wires via a strain induced lateral ordering process. Quantum wire (QWR) arrays were formed during the gas source molecular beam epitaxial (MBE) growth of (InP)2/(GaP)2 bilayer superlattices (BSLs) and were studied by time-resolved and linearly polarized cathodoluminescence. Nonlinear optical properties, such as phase-space filling effects, were observed to be indicative of the QWR nature of the samples. Samples prepared by gas source MBE were found to have a greater uniformity, smaller QWRs, and higher optical quality in comparison to those obtained by metal–organic chemical vapor deposition. Misfit dislocations also formed in one of the BSL samples, indicating a partial strain relaxation at the GaAs/InGaP and BSL/InGaP interfaces. The carrier relaxation, transport, and collection in the QWRs were studied with time-resolved cathodoluminescence.