Copper oxide composites were successfully synthesized by a catalyst-free method, plasma arc technology. The as-synthesized composites were characterized by x-ray diffraction, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and x-ray photoelectron spectroscopy. The analysis revealed a mixture of crystalline copper oxide (CuO), cuprous oxide (Cu2O) and copper (Cu) phases of the copper oxide composites constitute of irregularly spheroidal particlesµ with nanoparticles aggregate on the surface. Gas pressure during plasma arc process noticeably influences the composition and solar radiative properties of the composite materials. Among the samples studied, the composites synthesized with an arc current of 80 A and a pressure of 300 Torr exhibited the highest near infrared diffuse reflectance, providing a total solar reflectance of 22.96%. The mixed phase composition together with the nanostructures among the composites are considered to contribute to the excellent near infrared reflectance of copper oxide composites. Low reflectance in the visible region combined with high reflectance in the near infrared region make this composite material a good candidate for solar reflective coating which will demonstrate black appearance but keep a cool surface under solar irradiation.