A facile synthetic route was adopted in this study to construct plasmonic binary Bi/β-Bi 2 O 3 hybrids through a solvothermal-incomplete calcination process. As-synthesized samples were systematically characterized by X-ray diffraction patterns, X-ray photoelectron spectroscopy, UV-Vis diffuse reflectance spectroscopy, scanning electron microscopy, transmission electron microscopy, and N 2 adsorption-desorption. The calcination temperature exerted an important effect on the surface phase composition variation and binary Bi/β-Bi 2 O 3 hybrids were formed at the suitable temperature with an intimate contact between both components. These hybrids showed enhanced photocatalytic degradation efficiencies over dyes Rhodamine B and methyl orange, mainly attributing to the enlarged specific surface areas, favorable morphology and optical property, and the involvement of semimetal Bi with the surface plasmon resonance effect by means of improved visible-light absorption and efficient charge carries separation. In addition, active species entrapping experiments was eventually conducted for the sake of the possible photocatalysis mechanism speculation.