The composition distribution can influence the performances of laser cladding layers. Hence, the technology of rthe eal-time monitoring of chemical composition is required to apply on laser cladding process. In this experiment, four kinds of Ni-based alloy powders were used to prepare laser cladding layers on AISI (American Iron and Steel Institute) 4140 steel. At the same time, emission spectra were collected during real-time laser cladding process. The intensity of spectral lines were revised with a corrected number deduced with evaporation rate of elements. By correlating the weight ratios of elements with the intensity ratios of spectral lines, four calibration curves were established to monitor composition distribution. The main results are shown as following: Weight ratios among elements in the laser cladding layers changed versus input energy density due to different saturated vapor pressures among elements; the dilution amount of substrate showed weak relations under the different manufacturing parameters, and the main reason for this can be attributed to the change of thermo–physical properties among different Ni-based alloy powders; the predicted results showed that when the composition concentration was higher than 3 wt.%, the relative error was lower than 8%, compared with EDS (Energy-dispersive X-ray spectroscopy) testing data.