In this study, microparticle coatings and nanoparticle coatings were fabricated on copper surfaces by an electrochemical deposition method and an electrophoretic deposition method, respectively. Pool boiling of NOVEC-649 was experimentally studied on the coated surfaces, concerning heat transfer, bubble dynamics, and critical heat fluxes. Compared with a smooth surface, heat transfer coefficients and critical heat flux (CHF) were improved, achieving a maximum heat transfer enhancement of 460% on the nanoparticle-coated surface and a maximum CHF enhancement of 60% on the microparticle-coated surface. Based on high speed visualizations, bubble departure diameters were measured and compared with several correlations, and then the heat transfer was analyzed by a mechanistic model, considering natural convection, transient heat conduction and microlayer evaporation. The mechanistic model demonstrated a good ability to predict the present results. In addition, wickability, representing a liquid supplement ability, was measured, indicating that the wickability enhancement was probably responsible for the CHF improvement.