As an advanced connection technology for large thick-walled components, narrow gap laser welding has the advantages of small heat input and high efficiency and quality. However, porosity defects are prone to occur inside the weld due to the complex welding environment. In this study, the influence of the process parameters and pollutants such as water and oil on the porosity defect were explored. The action mechanism of water on the electron temperature and spectral intensity of the laser-induced plasma was analyzed. The results showed that the spectral intensity during narrow gap laser welding was weaker than that of flat plate butt welding. Under the optimal welding process conditions, the electron temperature during narrow gap laser self-fusion welding was calculated as 7413.3 K by the Boltzmann plot method. The electron density was 5.6714 × 1015 cm−3, conforming to the thermodynamic equilibrium state. With six groups of self-fusion welding parameters, only sporadic porosity defects were observed according to the X-ray detection. When there was water on the base metal surface, a large number of dense pores were observed on the weld surface and in the weld through X-ray inspection. Compared with the spectral data obtained under the normal process, the relative light intensity of the spectrometer in the whole band was reduced. The electron temperature decreased to the range of 6900 to 7200 K, while the electron density increased. The spectrum variation during narrow gap laser wire filling welding was basically the same as that of laser self-fusion welding. The porosity defects caused by water and oil pollutants in the laser welding could be effectively identified based on the intensity of the Fe I spectral lines.