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The breakup of Pangea fundamentally shaped modern continents and controlled the climatic distribution and biodiversity on Earth. Although our knowledge on the processes that control the assembly and breakup of supercontinents has significantly improved, the timing of supercontinent assembly and breakup initiation remains in some cases controversial. According to the available data, the assembly of Pangea was completed in middle Permian time, resulting in the formation of major orogenic belts and transform faults like the N–S‐trending, dextral, Caltepec fault in Mexico. Pangea breakup initiation is bracketed to early Middle Triassic time. In this work, we present new sedimentological, structural and U‐Pb geochronological data from a fluvial unit, the Matzitzi Formation of southern Mexico, the age and tectonic setting of which have remained an enigma for the past century. Our data document that the Matzitzi Formation is the stratigraphic record of a late Permian, anastomosing fluvial system that flowed in a—NNE‐trending extensional trough developed on top of the Caltepense belt, a transpressive belt formed along the Caltepec fault. We propose and discuss three possible scenarios for the tectonic setting of the Matzitzi Formation. In the first scenario, the unit is the stratigraphic record of the Caltepec fault late activity, which caused local NW–SE extension along the western margin of Pangea during its final assembly. In the second scenario, the Matzitzi Formation was deposited in an extensional basin formed by slab rollback along the western equatorial Pangea margin. In the third scenario, the extensional basin of the Matzitzi Formation was formed in the framework of the Pangea breakup. In this case, our data would suggest that Pangea breakup initiation must be dated back to late Permian time, which is ca. 15 m.y. older than the Middle Triassic age documented by the previous work. Considering that evidence of Permian extension has also been reported along the Appalachian belt, we suggest that the Matzitzi Formation was deposited during regional‐scale extension of western equatorial Pangea; therefore, we preliminarily support the third scenario. The distribution of Permian extension along suture belts developed during Pangea assembly highlights the fundamental role played by pre‐existent zones of weakness in the breakup of a supercontinent. [ABSTRACT FROM AUTHOR]