Silicon quantum dots embedded in an amorphous matrix of silicon carbide were realized by a magnetron co-sputtering process and post-annealing. X-ray photoelectron spectroscopy, glancing x-ray diffraction, Raman spectroscopy and high-resolution transmission electron microscopy were used to characterize the chemical composition and the microstructural properties. The results show that the sizes and size distribution of silicon quantum dots can be tuned by changing the annealing atmosphere and the atom ratio of silicon and carbon in the matrix. A physicochemical mechanism is proposed to demonstrate this formation process. Photoluminescence measurements indicate a multi-band configuration due to the quantum confinement effect of silicon quantum dots with different sizes. The PL spectra are further widened as a result of the existence of amorphous silicon quantum dots. This multi-band configuration would be extremely advantageous in improving the photoelectric conversion efficiency of photovoltaic solar cells.