The characterization of laser-induced breakdown spectroscopy (LIBS) near the gas–liquid two-phase interface was investigated with the laser acting on the sample along the horizontal direction. Simulation of the laser beam focusing process and observation of laser beam spot images show that difference in focusing positions in the air and the solution results from refraction of the laser beam entering the solution from the air and the change of propagation direction on the container lateral. The peak power and mean irradiance of the focused laser beam spot increase with the distance away from the interface, which is attributed to the fact that the loss of laser energy due to the refraction and reflection of light at the interface decreases with the focusing position moving away from the interface. This variation trend of laser irradiance allows for the growth of the spectral line intensity and lifetime with increasing the distance from the interface. The plasma electron density and temperature decrease with the delay time but increase with the distance away from the interface at the same delay time. Our findings help us to gain more insight into the characteristics and evolution mechanisms of LIBS produced near the gas–liquid two-phase interface, which provides theoretical guidance for the correction of LIBS spectra especially in water pollution monitoring. © 2022 Optica Publishing Group