Adding nanoparticles or surfactants to pure working fluid is a common and effective method to improve the heat transfer performance of pool boiling. The objective of this research is to determine whether additives have the same efficient impact on heat transfer enhancement of the non-azeotropic mixture. In this paper, Ethylene Glycol/Deionized Water (EG/DW) was selected as the representing non-azeotropic mixture, and a comparative experiment was carried out between it and the pure working fluid. In addition, the effects of different concentrations of additives on the pool boiling heat transfer performance under different heat fluxes were experimentally studied, including TiO2 nanoparticles with different particle diameters, different kinds of surfactants, and mixtures of nanofluids and surfactants. The experimental results showed that the nanoparticles deteriorated the heat transfer of the EG/DW solution, while the surfactant enhanced the heat transfer of the solution when the concentration closed to a critical mass fraction (CMC). However, the improvement effect was unsteady with the increase in the heat flux density. The experimental results suggest that the mass transfer resistance of the non-azeotropic mixture is the most important factor in affecting heat transfer enhancement. Solutions with 20 nm TiO2 obtained a steady optimum heat transfer improvement by adding surfactants.