This research aimed to evaluate the comparative biogas yields of waste (peels) of selected fibrous materials from the West African region: cassava, plantain, a mixture of cassava, plantain and yam. Three models: The Boyle model, the Modified Boyle’s model, and the Buswell and Müller’s model were used to determine the theoretical maximum biomethane potential (TBMP), while the Hohenheim Biogas Yield test (D-HBT) was used to undertake a batch test of anaerobic digestion. The samples were co-digested with digested sewage sludge (DSS) for 39 days, with an operating temperature of 37 ± 0.5 °C. The study draws comparisons between the TBMPs and the experimental results, the experimental results of the different substrates, and the experimental results and figures reported in the literature. From the experimental results, plantain peels had the highest biogas yield (468 ± 72 mL/g oTS), followed by a mixture of yam, cassava and plantain peels (362 ± 31 mL/g oTS) and cassava peels obtained the least biogas yield (218 ± 19 mL/g oTS). TBMPS of 204.04, 209.03 and 217.45 CH4 mL/g oTS were obtained for plantain peels, a mixture of yam, cassava and plantain peels and cassava peels, respectively, evaluated using Boyle’s model. For all the samples, the TBMPS (205.56, 209.03 and 218.45 CH4 mL/g oTS, respectively) obtained using the Buswell and Mueller model were slightly higher than those obtained by both the Boyle and the modified Boyle’s model (163.23, 167.22 and 174.76 CH4 mL/g oTS, respectively). While the study result is sufficient to imply that generating biogas from fibrous waste materials in its mixture form is a valuable approach, it is not sufficient to conclude that the use of these waste materials in its naturally occurring mixture form has a technical added advantage in co-digestion over their individual potential. However, future studies could explore this possibility with different fractions of the mixture with a view to optimising generation. The study finds that theoretically modelling the biogas potential of fibrous materials is a good method for biogas evaluation despite having overestimation tendencies, as this challenge could be corrected by applying factors that result in these tendencies, biodegradability indices. The data can, therefore, find use in fibrous waste treatment and waste-to-energy technologies, especially in Africa. This application will not be negatively affected by whether single waste streams are used or their mixture.