Quickly and accurately measuring the volume of large underground energy storage caverns is not only a method to test the scientific rationality of engineering design and construction achievement, it is also the basic requirement for energy storage and transportation engineering and the foundation of the dynamic control during operation depot. In order to quickly and accurately obtain the storage caverns volume and the elevation-cumulative volume curve in centimeter level, a laser sophisticated measurement system (LSMS) based on cross section and the corresponding data processing method are developed. The method is successfully applied in the volume measurement of underground energy storage caverns and the elevation-cumulative volume curve in centimeter level is achieved. The true volume is estimated by regression analysis and the volume measurement accuracy can reach -0.06%, which is one order of magnitude better than the regulatory requirements. Combined with the experimental data of total station and terrestrial 3D laser scanner, eight technical specifications are comparatively analyzed. The feasibility and correctness of the laser sophisticated measurement system and the corresponding data processing algorithm are verified.