Boiling heat transfer, utilizing latent heat during phase change, has widely been used due to its high thermal efficiency and plays an important role in existing and next-generation cooling technologies. The most critical parameter in boiling heat transfer is critical heat flux (CHF), which represents the maximum heat flux a heated surface can sustain during boiling. CHF is primarily influenced by the wicking performance, which governs liquid supply to the surface. This study experimentally and numerically analyzed the wicking performance of micropillar structures at various temperatures (20–95 °C) using distilled water as the working fluid to provide fundamental data for CHF prediction. Infrared (IR) visualization was used to extract the wicking coefficient, and the experimental data were compared with computational fluid dynamics (CFD) simulations for validation. At room temperature (20 °C), the wicking coefficient increased with larger pillar diameters (D) and smaller gaps (G). Specifically, the highest roughness factor sample (D04G10, r = 2.51) exhibited a 117% higher wicking coefficient than the lowest roughness factor sample (D04G20, r = 1.51), attributed to enhanced capillary pressure and improved liquid supply. Additionally, for the same surface roughness factor, the wicking coefficient increased with temperature, showing a 49% rise at 95 °C compared to 20 °C due to reduced viscous resistance. CFD simulations showed strong agreement with experiments, with error within ±10%. These results confirm that the proposed numerical methodology is a reliable tool for predicting wicking performance near boiling temperatures.