The detailed chemical kinetics of ethanol was reduced by means of path analysis and sensitivity analysis. The important components and reaction pathways of ethanol combustion were sorted out, and a reduced chemical kinetics model of ethanol containing 37 components and 78 reactions was developed. On the basis of the reduced mechanism of the gasoline surrogate [iso-octane, n-heptane, toluene, and diisobutylene (DIB)], the reduced mechanism of ethanol was then coupled. A reduced chemical kinetic model of a five-component (iso-octane, n-heptane, toluene, DIB, and ethanol) fuel containing 124 components and 244 reactions and suitable for homogeneous charge compression ignition (HCCI) combustion was finally obtained. Simulation results of the five-component reduced mechanism are compared with the ignition delay of four different components of gasoline surrogate under a shock tube. These results well matched the experimental value. At the same time, the simulation results of the model well matched the experimental results of combustion under HCCI engine conditions, showing that the model was suitable for the HCCI combustion simulation of gasoline.