In the present study, an electrophoretic deposition method was employed to modify copper surfaces with Cu-Zn (∼100 nm) nanoparticles. Pool boiling heat transfer of HFE-7200 on the modified surfaces was experimentally studied. The results showed that the heat transfer coefficient on the modified surfaces was significantly enhanced compared with that on a smooth surface, e.g., a maximum 100% enhancement, while the maximum superheat on the modified surfaces was around 20 K lower than that on the smooth surface. However, the critical heat flux (CHF) was not improved considerably, and supplementary tests indicated that the wickability of HFE-7200 was almost the same on the modified surfaces and the smooth surface. The departure diameters of bubbles were recorded by a high speed camera, which were compared with several models in literature. Active nucleation site sizes were evaluated by the Hsu nucleation theory and active nucleation site densities were estimated by appropriate correlations. In addition, a heat transfer model, considering natural convection, re-formation of thermal boundary layer and microlayer evaporation, was formulated to predict the heat transfer on the modified surfaces and the smooth surface. A relatively good prediction was achieved.