The interface chemical composition of heterostructured GaP-GaAs nanowire segments was studied by the use of energy-dispersive x-ray analysis. An arsenic-rich tail in the GaP segments following GaAs could be minimized by reducing the AsH(3) molar fraction and the growth rate. For the temperature regime used for vapour-liquid-solid growth, we observe the opposite trend on interface sharpness compared to high-temperature layer-by-layer