The Democratic Republic of the Congo holds important reserves of oil shale which is still under geological status. Herein, the characterization and pyrolysis kinetics of type I kerogen-rich oil shale of the western Central Kongo (CK) were investigated. X-ray diffraction, Fourier-transform infrared spectroscopy and thermal analysis (TG/DTA) showed that CK oil shale exhibits a siliceous mineral matrix with a consistent organic matter rich in aliphatic chains. The pyrolysis behavior of kerogen revealed the presence of a single mass loss between 300 and 550 °C, estimated at 12.5% and attributed to the oil production stage. Non-isothermal kinetics was performed by determining the activation energy using the iterative isoconversional model-free methods and exhibits a constant value with E = 211.5 ± 4.7 kJ mol−1. The most probable kinetic model describing the kerogen pyrolysis mechanism was obtained using the Coats–Redfern and Arrhenius plot methods. The results showed a unique kinetic triplet confirming the nature of kerogen, predominantly type I and reinforcing the previously reported geochemical characteristics of the CK oil shale. Besides, the calculation of thermodynamic parameters (ΔH*, ΔS* and ΔG*) corresponding to the pyrolysis of type I kerogen revealed that the process is non-spontaneous, in agreement with DTA experiments.