The present research investigates the behaviour of sustainable Self-Compacting Concrete (SCC) when subjected to high temperatures, focusing on workability, post-fire impact resistance, and the effects of fire protection coatings. To develop environmentally friendly SCC mixes, Supplementary Cementitious Materials (SCM) such as Fly Ash (FA), Ground Granulated Blast Furnace Slag (GGBFS), and Expanded Perlite Aggregate (EPA) were used. Fifty-six cubes and ninety-six impact SCC specimens were cast and cured for testing. Fire-resistant Cement Perlite Plaster (CPP) coatings were applied to the protected specimens, a passive protection coating rarely studied. SCC (unprotected and protected) specimens, i.e., protected and unprotected samples, were heated following the ISO standard fire curve. An extensive comparative study has been conducted on utilising different SCMs for developing SCC. Workability behaviour, post-fire impact resistance, and the influence of fire protection coatings on sustainable SCC subjected to high temperatures are the significant parameters examined in the present research, including physical observations and failure patterns. The test results noted that after 30 min of exposure, the unprotected specimen exhibited a significant decrease in failure impact energy, ranging from 80% to 90%. Furthermore, as the heating duration increased, there was a gradual rise in the loss of failure impact energy. However, when considering the protected CPP specimens, it was observed that they effectively mitigated the loss of strength when subjected to elevated temperature. Therefore, the findings of this research may have practical implications for the construction industry and contribute to the development of sustainable and fire-resistant SCC materials.