Titanite is a valuable tool for studying polymetamorphism and understanding the evolution of orogenic belts as it potentially records different stages of metamorphic evolution. The combination of geochronology and Zr-in-titanite geothermometry has been widely used in petrochronology studies. However, there is ongoing debate regarding the significance of ages and temperatures obtained from titanite. Here, we conducted the first integrated titanite, zircon, and apatite UPb study, along with Zr-in-titanite geothermometry, on calc-silicate rocks from a polymetamorphic complex of the central Dom Feliciano Belt (Western Gondwana). Our aim was to investigate the impact of various metamorphic events on titanite grains. We carried out a geochronological, geochemical, and petrographic analysis of a calc-silicate sequence of the Passo Feio Complex, which was intruded by the Caçapava do Sul Granitic Complex (CSGC). The metamorphic complex experienced regional, contact, and hydrothermal metamorphism during the Neoproterozoic, but the ages and conditions of these metamorphic events remain widely debated. UPb analyses on over one hundred titanite grains from a K-feldspar-diopside schist revealed three distinct titanite populations. The older group, dated at 639 ± 3/7 Ma (2s; n = 19), was associated with the regional metamorphism event (M1), likely initiated by the primary collision of the Dom Feliciano Belt. The intermediate group exhibited an age of 596 ± 1/6 Ma (2s; n = 91). Given the presence of high-K magmatism and a carbonatite intrusion in the study area, producing zircon UPb ages around 600 Ma, this group was associated with contact metamorphism (M2), belike influenced by these intrusive igneous activities. The youngest titanite population showed an age of 566 ± 3/6 Ma (2s; n = 6), which closely aligns, within analytical error, with the age of 561 ± 1/6 Ma (2s; n = 46) obtained from UPb dating on apatite sourced from a diopside-phlogopite schist. The younger ages observed in both titanite and apatite are attributed to alterations resulting from interactions with hydrothermal fluids (M3) during the cooling phase of the CSGC. Chemical analyses conducted with an electron microprobe assessed the Zr concentrations in fifty titanite grains, examining both bright and dark zones observed in back-scattered electron images. The lowest temperature recorded among the 50 grains was 629 °C, which corresponds to dark BSE zones. In the light zones, the minimum temperature was 639 °C. While temperatures estimated using the Zr content in titanite may not correspond precisely with UPb ages, combining titanite ages with those from other accessory minerals like zircon and apatite, along with microstructural analysis, can provide a more comprehensive understanding of orogenic belt evolution.