Boiling heat transfer enhancement via compound effect of the electrohydrodynamic (EHD) effect and microstructured surfaces has been experimentally and analytically investigated. A fluorinated dielectric liquid (Asahi Glass Co., Ltd., AE-3000) was selected as the working fluid. Pool boiling heat transfer in the saturated liquid was measured at atmospheric pressure. Microstructured surfaces, which are mainly used for cutting tools, were developed with diamond particles using electrodeposition technique. Four different particle diameters were prepared: 5, 10, 15, and a mixture of 5 and 1.5 μm. The critical heat flux (CHF) for diamond particle surfaces showed 27–30 W/cm2 which was 26–40% increase for comparing with a noncoated surface (21.5 W/cm2). Upon application of a −5 kV/mm electric field to the microstructured surface (a mixture of 5 and 1.5 μm particles), a CHF of 70.2 W/cm2 at a superheat of 21.7 K was obtained. The previous theoretical equation of pool boiling predicted the CHF with electric field and without the electrode within 10%. Also, the CHF enhanced by the diamond coated surfaces was correlated well with the contact angle.