A laser induced breakdown spectroscopy-based apparatus for the analysis of element, employing a 532 nm laser and a multi-channel optical spectrometer with a non-intensified CCD array, has been built and tested. It was applied to analyze the carbon content of coal fly ash. Seven groups of pulse laser in the range of 35 to 98 mJ were used to ablate the fly ash samples. The electron densities and plasma temperatures with different laser energy were determined, and the influence of laser energy on the intensity of analysis carbon lines was also analyzed. The results show that carbon line intensity increases slowly with the increase in laser energy in the range of 35 to 46 mJ, and increases fast in the range of 46 to 78 mJ, then trends to saturation and has a little drop. At the same time, air breakdown has increased significantly, and has an obvious effect on sample plasma. Furthermore, the electron density and plasma temperature increase with the laser energy until 78 mJ and then begin to decrease. It indicates that a proper laser energy can enhance the plasma emission signal, and avoid the negative impact of air breakdown that prevent the pulse laser from reaching the surface of sample and ablating it. In this experiment situation, the measurement accuracy of the carbon line can be improved.