Spherical Cu nanocavity surfaces are synthesized to examine the individual role of contact angles in connecting lateral Rayleigh-Taylor wavelength to vertical Kevin-Helmholtz wavelength on hydrodynamic instability for the onset of pool boiling Critical Heat Flux (CHF). Solid and porous Cu pillar surfaces are sintered to investigate the individual role of pillar structure pitch at millimeter scale, named as module wavelength, on hydrodynamic instability at CHF. Last, spherical Cu nanocavities are coated on the porous Cu pillars to create a multiscale Cu structure, which is studied to examine the collective role and relative significance of contact angles and module wavelength on hydrodynamic instability at CHF, and the results indicate that module wavelength plays the dominant role on hydrodynamic instability at CHF when the height of surface structures is equal or above ¼ Kelvin-Helmholtz wavelength. Pool boiling Heat Transfer Coefficient (HTC) enhancements on spherical Cu nanocavity surfaces, solid and porous Cu pillar surfaces, and the integrated multiscale structure have been investigated, too. The experimental results reveal that the nanostructures and porous pillar structures can be combined together to achieve even higher enhancement of HTC than that of individual structures.