Abstract Our previous research, honoring interfacial properties, revealed that the wettability state is predominantly caused by phase change—transforming liquid phase to steam phase—with the potential to affect the recovery performance of heavy-oil. Mainly, the system was able to maintain its water-wetness in the liquid (hot-water) phase but attained a completely and irrevocably oil-wet state after the steam injection process. Although a more favorable water-wetness was presented at the hot-water condition, the heavy-oil recovery process was challenging due to the mobility contrast between heavy-oil and water. Correspondingly, we substantiated that the use of thermally stable chemicals, including alkalis, ionic liquids, solvents, and nanofluids, could propitiously restore the irreversible wettability. Phase distribution/residual oil behavior in porous media through micromodel study is essential to validate the effect of wettability on heavy-oil recovery. Two types of heavy-oils (450 cP and 111,600 cP at 25C) were used in glass bead micromodels at steam temperatures up to 200C. Initially, the glass bead micromodels were saturated with synthesized formation water and then displaced by heavy-oils. This process was done to exemplify the original fluid saturation in the reservoirs. In investigating the phase change effect on residual oil saturation in porous media, hot-water was injected continuously into the micromodel (3 pore volumes injected or PVI). The process was then followed by steam injection generated by escalating the temperature to steam temperature and maintaining a pressure lower than saturation pressure. Subsequently, the previously selected chemical additives were injected into the micromodel as a tertiary recovery application to further evaluate their performance in improving the wettability, residual oil, and heavy-oil recovery at both hot-water and steam conditions. We observed that phase change—in addition to the capillary forces—was substantial in affecting both the phase distribution/residual oil in the porous media and wettability state. A more oil-wet state was evidenced in the steam case rather than in the liquid (hot-water) case. Despite the conditions, auspicious wettability alteration was achievable with thermally stable surfactants, nanofluids, water-soluble solvent (DME), and switchable-hydrophilicity tertiary amines (SHTA)—improving the capillary number. The residual oil in the porous media yielded after injections could be favorably improved post-chemicals injection; for example, in the case of DME. This favorable improvement was also confirmed by the contact angle and surface tension measurements in the heavy-oil/quartz/steam system. Additionally, more than 80% of the remaining oil was recovered after adding this chemical to steam. Analyses of wettability alteration and phase distribution/residual oil in the porous media through micromodel visualization on thermal applications present valuable perspectives in the phase entrapment mechanism and the performance of heavy-oil recovery. This research also provides evidence and validations for tertiary recovery beneficial to mature fields under steam applications.