A novel, high-temperature, thermally conductive, microporous coating (HTCMC) is developed by brazing copper particles onto a copper surface. This coating is more durable than many previous microporous coatings and also effectively creates re-entrant cavities by varying brazing conditions. A parametric study of coating thicknesses of 49–283 μm with an average particle size of ∼25 μm was conducted using the HTCMC coating to understand nucleate boiling heat transfer (NBHT) enhancement on porous surfaces. It was found that there are three porous coating regimes according to their thicknesses. The first regime is “microporous” in which both NBHT and critical heat flux (CHF) enhancements gradually grow as the coating thickness increases. The second regime is “microporous-to-porous transition” where NBHT is further enhanced at lower heat fluxes but decreases at higher heat fluxes for increasing thickness. CHF in this regime continues to increase as the coating thickness increases. The last regime is named “porous,” and both NBHT and CHF decrease as the coating thickness increases beyond that of the other two regimes. The maximum NBHT coefficient observed was ∼350,000 W/m2K at 96 μm thickness (microporous regime) and the maximum CHF observed was ∼2.1 MW/m2 at ∼225 μm thickness (porous regime).