Selective laser melting (SLM) technology is a promising additive manufacturing technology. However, due to the numerous influencing factors in this complex process, a reliable real-time method is needed to monitor the forming process of SLM. The molten pool is the smallest forming unit in the SLM process, the consistency of which can effectively reflect the quality of the printing process. By using a coaxial optical path structure and a compound amplifier circuit, high-speed acquisition of molten pool radiation can be realized. Next, single factor analysis and orthogonal experimentation were used to investigate the influence levels of key process parameters on the radiation of molten pool. In addition, numerical simulation was carried out with the same parameter setting schemes, the results of which are consistent with those in radiation detection experiments. It is shown that the laser power has the greatest effect on the radiation of the molten pool, while the scanning speed and the hatch spacing have little effect on the radiation. Finally, the positioning experiment involving the small hole structure was carried out, and the experimental results showed that the device could accurately locate the position coordinates of the given hole structure.