Avalanche photodetectors (APDs) are key components in optical communication systems due to their increased photocurrent gain and short response time as compared to conventional photodetectors. A detector design where the multiplication region is implemented in a large band gap material is desired to avoid detrimental Zener tunneling leakage currents, a concern otherwise in smaller band gap materials required for absorption at 1.3/1.55 μm. Self-assembled III-V semiconductor nanowires offer key advantages such as enhanced absorption due to optical resonance effects, strain-relaxed heterostructures, and compatibility with mainstream silicon technology. Here, we present electrical and optical characteristics of single InP and InP/InAsP nanowire APD structures. Temperature-dependent breakdown characteristics of p⁺-n-n⁺ InP nanowire devices were investigated first. A clear trap-induced shift in breakdown voltage was inferred from I-V measurements. An improved contact formation to the p⁺-InP segment was observed upon annealing, and its effect on breakdown characteristics was investigated. The band gap in the absorption region was subsequently varied from pure InP to InAsP to realize spatially separate absorption and multiplication APDs in heterostructure nanowires. In contrast to the homojunction APDs, no trap-induced shifts were observed for the heterostructure APDs. A gain of 12 was demonstrated for selective optical excitation of the InAsP segment. Additional electron-beam-induced current measurements were carried out to investigate the effect of local excitation along the nanowire on the I-V characteristics. Simulated band profiles and electric field distributions support our interpretation of the experiments. Our results provide important insight for optimization of avalanche photodetector devices based on III-V nanowires. © 2017 American Chemical Society