The near resonant energy transfer from SiO(b3П) to Na is one of the most important processes of the chemical sodium atom laser. In order to research the process, an experimental device of near resonant energy transfer, which includes a system of synthesizing SiO(b3П) and a system of producing and carrying sodium vapor, was set up. The metastable state energy storage particle—SiO(b3П) was synthesized by the reaction of products of silane pyrolysis and N2O. Based on these works, the experimental research of energy transfer from SiO(b3П) to Na has been done. The spontaneous emission spectra of SiO(b3П) and Na(4d2D) was detected; the existence of the near resonant energy transfer from SiO(b3П) to Na and the existence of Na(4d2D) were testified. The further research showed that under the experimental conditions of the flow rate of SiH4 at 0.09 mmol/s, the flow rate of SiH4 buffer gas at 14.88 mmol/s, the flow rate of N2O at 0.744 mmol/s, and the pyrolysis temperature of SiH4 at 1350 K, when the flow rate of Na buffer gas (7.44 mmol/s) is fixed, the density of Na(4d2D) increases with the rise of the temperature of Na oven; and when the temperatures of Na oven (673 K and 723 K respectively) are fixed, the density of Na(4d2D) increases with the rise of the flow rate of Na buffer gas almost linearly. This work provides a preparation for the further research of this laser system, such as the measurement of signal gain and performance of lasing.