Some surrogate fuel models have been formulated based on gaseous combustion properties. While development of surrogate fuel for spray combustion is still in an exploratory stage, it is in a great demand to develop methods to validate the volatility performance and corresponding combustion properties of a surrogate fuel mixture based on real fuel’s behavior. Distillation experiment of Chinese aviation fuel RP-3 was carried out to reveal evolution of components and chemical functional groups during the vaporization process of a real fuel. Both liquid and vapor samples were analyzed using GC-MS and NMR. The variation of functional groups and volatility performance of surrogate were also investigated using a well-validated numerical model. The experimental results show that the chemical functional groups almost have no change and that the average carbon number in the gas phase increases throughout the distillation. On contrary, the functional groups of some existing surrogates varied greatly during their distillation processes in spite that their distillation curves match well with real fuel’s. A 24-component mixture is formulated to demonstrated possibility to match both distillation behavior and combustion properties during vaporization. This study provides some potential directions for developing a surrogate with its vaporization truthfully representing the vaporization of the target real fuel.