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The study across the Pliensbachian–Toarcian boundary sedimentary record in the Bizanet section of the Pyrenean Basin (southern France) revealed the presence of solid bitumen. This secondary organic matter was characterized using petrographic (transmitted and reflected white lights, incident blue light, and scanning electron microscopy) and geochemical (total organic carbon, total sulfur, and insoluble residue) techniques. The spore coloration index (SCI) was also determined. With the characterization of the optical properties and reflectance of the solid bitumen, it was possible to distinguish four different families (A–D) that display a wide range of reflectance values, from 0.21% to 2.64% BRr, i.e., from glance pitch to meso-impsonite. SCI values were higher than 9–9.5 (%Req > 1.50%). The comparison between the equivalent vitrinite reflectance values of the solid bitumen and SCI showed that this index and the solid bitumen D values are concordant, indicating that solid bitumen D can be considered an indigenous bitumen. The other three families of solid bitumen (A–C) are considered as having migrated. The laterally equivalent Pont de Suert section (South Pyrenean Zone) displays no trace of solid bitumen which points to the important role of the morphotectonic context of the Bizanet section in the migration of these hydrocarbons, namely, the presence of a major thrust fault in the eastern Corbières close to the section’s location.