To ensure adequate reliability in two-phase cooling systems involving boiling, it is essential to enhance the heat transfer coefficient and maximize the critical heat flux (CHF) limit. A key technique to avoid surface burnout and increase the CHF limit in pool boiling is the frequent coolant supply to the probable dry-out locations. In the present work, we have explored the plasma-spray coating as a surface modification technique for enhancing heat transfer coefficient and CHF value in pool boiling applications. Three plasma-coated aluminum surfaces (C-15, C-20, and C-25) are fabricated on a copper substrate at three different plasma powers of 15, 20, and 25 kW, respectively. Detailed surface morphologies of the plasma-sprayed coatings are presented, and their roles in pool boiling heat transfer mechanisms are analyzed. Plasma-coated surfaces exhibit wickability characteristics and enhanced wettability compared to the plain copper surface. Saturated pool boiling experiments are performed with DI (deionized) water at atmospheric pressure. Plasma spray-coated surfaces show favorable boiling incipience with less wall superheat and more active nucleation sites than the plain copper surface. Compared to the plain copper surface, enhancement values of nearly 68, 60.7, and 55.5% in the heat transfer coefficient are observed for C-15, C-20, and C-25 plasma-coated surfaces, respectively. Experiments could not be performed beyond the heat flux of 197 W/cm2 due to repeated failure of the cartridge heaters. Based on the experimental measurement of wickabilities, the CHF values of plasma-coated surfaces have been theoretically calculated. Compared to the plain copper surface, a maximum 2.39 times higher CHF value is observed for C-15 plasma-coated surface. Improved wettability and wickability are responsible for CHF enhancement in the case of plasma-coated surfaces. At higher heat flux, capillary wicking and frequent rewetting of the dryout locations delay the burnout phenomenon, enhancing CHF in plasma-coated surfaces. The plasma-spray coating is a robust and scalable process, which can be a potential candidate for high heat flux dissipation in various industrial applications.