We investigated nucleate boiling heat transfer with precisely controlled wetting patterns and micro-posts, to gain insights into the impact of surface heterogeneity. To create heterogeneous wetting patterns, self-assembled monolayers (SAMs) were spatially patterned. Even at a contact angle <90°, bubble nucleation and bubble frequency were accelerated on SAM patterns, since this contact angle is larger than that found on plain surfaces. Micro-posts were also fabricated on the surface, which interrupted the expansion of generated bubbles. This surface structuring induced smaller bubbles and higher bubble frequency than the plain surface. The resistance provided by surface structures to bubble expansion broke the interface between the vapor mushroom and the heating surface, and water could therefore be continuously supplied through these spaces at high heat flux. To induce synergistic effects with wetting patterns and surface structures on boiling, we fabricated SAM patterns onto the heads of micro-posts. On this combined surface, bubble nucleation was induced from the head of the micro-posts, and bubble growth was influenced by both the SAM pattern and the micro-post structures. In particular, separation of the vapor path on the SAM patterns and the liquid path between micro-post structures resulted in high heat transfer performance without critical heat flux deterioration.