© 2016, Higher Education Press and Springer-Verlag Berlin Heidelberg. In the present work, the synthesis of micro- and nano-sized spheres of metallic bismuth by microwave-assisted solvothermal method is reported. The synthesis method was carried out at different power levels and at a unique frequency of microwave irradiation. The sphere sizes were controlled by the microwave power level and the concentration of dissolved precursor. Structural and morphological characterization was performed by SEM, HRTEM, EELS and XRD. The results demonstrated that rhombohedral zero valent Bi spheres were synthesized after microwave radiation at 600 and 1200 W. However, if the power level is decreased to 120W, a monoclinic phase of Bi2O3 is obtained with a flake-like morphology. In comparison with a conventional hydrothermal process, the microwave-assisted solvothermal approach provides many advantages such as shorter reaction time, optimum manipulation of morphologies and provides a specific chemical phase and avoids the mixture of structural phases and morphologies which is essential for further applications such as drug delivery or functionalization with organic materials, thanks to its biocompatibility.