The dust from pulverized coal weakens the acquired signal and increases the analysis difficulty for the quantitative analysis of the carbon content of pulverized coal when using laser-induced breakdown spectroscopy (LIBS). Moreover, there is a serious matrix effect and a self-absorption phenomenon. To improve the analysis accuracy, the DSC-PLS (double spectral correction-partial-least-squares) method was proposed to predict the carbon content of pulverized coal. Initially, the LIBS signal was corrected twice using P-operation-assisted adaptive iterative-weighted penalized-least-squares (P-airPLS), plasma temperature compensation, and spectral normalization algorithms. The goodness of fit of the carbon element was improved from nonlinearity to above 0.948. The modified signal was then used to establish DCS-PLS models for predicting unknown samples. In comparison to the conventional PLS model, the DSC-PLS method proposed in this paper significantly improves the ability to predict carbon content. The prediction error of the developed method was dropped from an average of 4.66% to about 0.41%, with the goodness of fit R² of around 0.991.