Fly ash contents can be considered as a basis for optimal and stable boiler combustion control and fly ash quality control in power plant, especially the unburned carbon in fly ash. The real-time and quantitative measurement of contents in fly ash was studied using a constructed two-stage cyclone measurement system and detected using laser-induced breakdown spectroscopy(LIBS) technique. The surrounding gas effect, such as CO2 effect on unburned carbon content, was studied comprehensively in this paper. The CO2 effect was eliminated using this proposed combination method of two-stage cyclone measurement system and LIBS with 1ns pulse-width laser according to the efficient gas-particle separation and the controlled laser-induced plasma processes of particle flow. The quantitative analysis was improved using the plasma temperature correction method with the intensity ratio of the emission pair from magnesium as a plasma temperature indicator. The measurement of unburned carbon content in fly ash with temperature correction method presented the concordant results analyzed by chemical analysis method. It is demonstrated the feasibility and improved detection ability for the real-time measurement of fly ash contents in power plant