The amalgamation and breakup of the West Gondwana shaped the South American platform. The dynamics during the processes can be reflected by crust anisotropy of the platform, but there are no specialized crustal anisotropic measurements yet. Splitting analysis of Mohoconverted shear waves in P-wave receiver functions (Pms) can reveal crustal-scale anisotropy, which is important for understanding the dynamic evolution of the crust and for the interpretation of mantle anisotropy from splitting analysis of core–mantle refracted shear waves (XKS phases). This study measured crustal anisotropy for the old and stable South American platform by Pms splitting analysis. The splitting times vary mainly in the range of 0–0.5 s, with a regional mean of 0.2 s, slightly lower than that observed in tectonically active regions. The detected crustal anisotropy shows distinct characteristics and spatial zoning, providing insights into tectonic processes. (1) Fast polarization directions at stations close to the Transbrasiliano Lineament (TBL) are oriented NNE–SSW, generally consistent with the strike of the TBL but inconsistent with the maximum horizontal compressive stress, implying that they might be formed by dynamic metamorphism during the formation of the TBL. (2) Crustal anisotropy along the passive continental margin in the east and northeast is weak. Still, the fast polarization directions tend to be oriented along the margin, implying the existence of fossil extensional crustal fabrics formed during the continental rifting of West Gondwana. (3) The Paraná Basin, one of the world’s largest Large Igneous Provinces (LIP) covered by continental flood basalts, shows distinctively strong anisotropy, with fast polarization directions highly aligned with mantle anisotropy, implying that synchronous crust–mantle deformation occurred in these regions as a result of magmatism during the breakup of West Gondwana.