The Rio Muni Basin is a hotspot for deep-water oil exploration in West Africa. The discovery of thirteen oil and gas fields, including Ceiba, Akom 1, and Oveng, proves the basin’s excellent exploration prospects, but only limited research has thus far been carried out there. The recent new drilling indicates that there are organic matter-rich fine-grained sedimentary rocks in the Albian and Cenomanian–Turonian stages of the Cretaceous strata. However, the depositional models of organic-rich, fine-grained sedimentary rocks are not clear. The main objectives of this study are as follows: (1) to identify the lithofacies characteristics of fine-grained sedimentary rocks in the Albian–Turonian stages of the Rio Muni Basin; and (2) to establish a depositional model for organic-rich fine-grained sediments. In this study, the mineralogical characteristics of Albian–Turonian fine-grained were determined by means of X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM), and thin section analysis. In addition, the integration of mineralogical features with the total organic carbon (TOC) content allows for the recognition of three distinct lithofacies: (1) siliceous-clayey rock, (2) terrigenous clastic mixed fine-grained rock, and (3) lime-mixed fine-grained rock. Based on the evolutionary history of the passive continental margin basins in West Africa and the lithofacies characteristics, the deposition mode of organic-rich fine-grained sedimentary rocks in the Albian–Turonian stages was reconstructed by combining geochemical features with the characteristics of framboidal pyrite. The depositional models for the Albian stage are “continental margin–restricted sea–marine algae–source rocks” with the development of organic-rich fine-grained sedimentary rocks. The depositional models for the Cenomanian–Turonian stage are “continental margin–semiopen sea–mixed-source rocks”. The Albian and Cenomanian–Turonian organic-rich fine-grained sedimentary rocks represent two different deposition modes with restricted sea and semiopen sea conditions. The sedimentary characteristics in the study area during the two periods were both inherited and notably different.