Phase change heat transfer, crucial in thermal management systems, can be significantly enhanced through optimized surface structures. This study investigates pool boiling heat transfer enhancement using 3D printed structures with carefully designed pillar and pit geometries. We present a novel approach combining the Dual Rise model with separate liquid–vapor pathways to improve Critical Heat Flux (CHF) and Heat Transfer Coefficients (HTC). Using copper-infused Polylactic Acid (PLA) filaments, we created and sintered structured surfaces featuring pit-assisted nucleation sites, interpillar spacing for vapor escape, and pillar roughness for enhanced liquid supply. Experiments with deionized water and ethanol under atmospheric pressure demonstrated substantial improvements over plain surfaces: water showed an 87% increase in CHF and 39% in maximum HTC, while ethanol exhibited even greater enhancements of 122% in CHF and 61% in HTC. These improvements are attributed to the synergistic effects of optimized surface geometry and separated liquid–vapor pathways, reducing counterflow resistance and improving hydrodynamic stability. A theoretical framework based on the Dual Rise model explains these enhancements, providing insights into coupled capillary action and hemiwicking effects in boiling heat transfer. The study introduces predictive models for CHF and HTC enhancement, offering valuable tools for future design optimization in applications ranging from electronics cooling to power plant thermal management and advanced heat exchangers.