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Abstract Control over the distribution of dopants in nanowires is essential for regulating their electronic properties, but perturbations in nanowire microstructure may affect doping. Conversely, dopants may be used to control nanowire microstructure including the generation of twinning superlattices (TSLs)—periodic arrays of twin planes. Here the spatial distribution of Be dopants in a GaAs nanowire with a TSL is investigated using atom probe tomography. Homogeneous dopant distributions in both the radial and axial directions are observed, indicating a decoupling of the dopant distribution from the nanowire microstructure. Although the dopant distribution is microscopically homogenous, radial distribution function analysis discovered that 1% of the Be atoms occur in substitutional-interstitial pairs. The pairing confirms theoretical predictions based on the low defect formation energy. These findings indicate that using dopants to engineer microstructure does not necessarily imply that the dopant distribution is non-uniform.