In order to fuse airborne LiDAR scanning (ALS) and high resolution image for land cover classification, modeled LiDAR waveform that based on elevation information was integrated with CCD image three band (RGB) data in complex mountainous area. Verification experiment results showed that high accuracy for several typical land cover types classification in complex mountainous area could be acquired by the method. Moreover, the classification result of study area which located in Huangshan, Anhui Province was used to compare with the GlobeLand30 classification result to verify the method. The entire coverage of study area were classified into four landcover types (farmland, forest, water and village) by characteristic curves that combined modeled waveform with intensity and RGB information through artificial neural network (ANN). The result showed that the overall accuracy of study area classification was 95.22%, and Kappa coefficient was 0.9192. Compared with GlobeLand30 classification result accuracy (overall accuracy was 79.56% with Kappa coefficient of 0.6618) in this area, the research results was improved significantly.