Recent destructive earthquakes in Turkey (2023) with devastating effects have reawakened the discussion about seismic activity in Brazil and the vulnerability of the Brazilian buildings. Despite the lower magnitudes, national records should not be disregarded, as earthquakes with a magnitude below five may still cause loss of life and property damage. The assessment of existing RC buildings allows us to understand the performance of a structure during an earthquake and the adoption of mitigating measures. This paper preliminarily investigates the seismic vulnerability of the Metropolitan Cathedral in Brasilia, which was recognized as a World Heritage Site by ONU in 1987. The Rapid Visual Screening (RVS) procedure has been adopted for qualitative vulnerability assessment through the guidelines of the Japan Building Disaster Prevention Association at the procedure updated in accordance with the Brazilian reality. This research examined the structure under horizontal acceleration defined by national seismic code, and various scenarios are assumed as time aging, structural irregularities, and the level of importance of the structure. In this study, the Monte Carlo simulation is carried out to evaluate the level of safety. A performed analysis has shown that the examined building possesses the seismic capacity required against the expected earthquake motions. Even with reliability analysis, the structure achieves an acceptable level of safety. The results highlight the importance of a probabilistic approach to make reliable decisions on the conservation and rehabilitation of architectural heritage buildings.