A benchtop laser-induced breakdown spectroscopy is demonstrated to determine the elemental carbon content present in raw coal used for combustion in power plants. The spectral intensities of molecular CN and C2 emission are measured together with the atomic carbon (C) and other inorganic elements (Si, Fe, Mg, Al, Ca, Na, and K) in the laser-induced breakdown spectroscopy spectrum of coal. The emission persistence time of C2 molecule emission is measured from the coal plasma generated by a nanosecond laser ablation with a wavelength of 266 nm in the Ar atmosphere. The emission persistence time of molecular C2 emission along with the spectral intensities of major ash elements (Fe, Si, Al, and Ca) and carbon emissions (atomic C, molecular CN, and C2) shows a better relationship with the carbon wt% of different coal samples. The calibration model to measure elemental carbon (wt%) is developed by combining the spectral characteristics (spectral intensity) and the temporal characteristics (emission persistence time of C2 molecule emission). The temporal characteristic studies combined with the spectroscopic data in the partial least square regression model have resulted in an improvement in the root mean square error of validation, and the relative standard deviation is reduced from 10.8% to 4.1% and from 11.3% to 6.0%, respectively. © The Author(s) 2021.