Gold-peapodded Ga2O3 nanowires were fabricated successfully in a well-controlled manner by thermal annealing of core shell gold Ga2O3 nanowires. During the heating process, the core gold nanowires were broken up into chains of nanoparticles at sufficiently high temperature by the mechanism of Rayleigh instability. In addition, the size, shape, and interspacing between the particles can be manipulated by varying the annealing time and/or the forming gas. The plasmonic behaviors of these nanostructures are investigated by optical spectroscopy. A single nanowire optical device was designed, and its photonic characteristics were investigated. A remarkably high on/off photocurrent ratio in response to a 532 nm Nd:YAG laser light was found. As the size of the particle (pea) increases, the corresponding spectra are red-shifted. In addition, morphological changes of the peas lead to a distinct spectral response. The results may usher in the diverse applications in optoelectronics and biosensing devices with peapod nanostructures.