Rapid online analysis of liquid slag is essential for optimizing the quality and energy efficiency of steel production. To investigate the key factors that affect the online measurement of refined slag using laser-induced breakdown spectroscopy (LIBS), this study examined the effects of slag composition and temperature on the intensity and stability of the LIBS spectra. The experimental temperature was controlled at three levels: 1350 °C, 1400 °C, and 1450 °C. The results showed that slag composition and temperature significantly affected the intensity and stability of the LIBS spectra. Increasing the Fe content and temperature in the slag reduces its viscosity, resulting in an enhanced intensity and stability of the LIBS spectra. Additionally, 42 refined slag samples were quantitatively analyzed for Fe, Si, Ca, Mg, Al, and Mn at 1350 °C, 1400 °C, and 1450 °C. The normalized full spectrum combined with partial least squares (PLS) quantification modeling was used, using the Ca II 317.91 nm spectral line as an internal standard. The results show that using the internal standard normalization method can significantly reduce the influence of spectral fluctuations. Meanwhile, a temperature of 1450 °C has been found to yield superior results compared to both 1350 °C and 1400 °C, and it is advantageous to conduct a quantitative analysis of the slag when it is in a “water-like” state with low viscosity.