Biomass is the most utilized form of renewable energy, especially in developing nations, and is a possible replacement for fossil fuel in power generation. The most commonly used method for recovering energy from biomass is combustion. Many countries are exploring the utilization of energy crops and indigenous residues to deliver sustainable sources of biomass. For these bio-resources, detailed characterization of the fuel properties is essential in order to optimize the combustion processes. In this study, some potential energy crops and woods from Nigeria, namely Terminalia superba, Gmelina arborea, Lophira alata, Nauclea diderrichii, and also one abundant agricultural residue, palm kernel expellers (PKE), were characterized for their combustion properties. Standard characterization methods such as proximate and ultimate analyses, metals analysis, and ash fusion test were used for this purpose and the results were compared with some U.K. biomass. In addition, their thermal conversion was assessed by thermogravimetric analysis and pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS). Finally, combustion studies were conducted by suspending single biomass particles in a methane flame to obtain information on reactivities and combustion characteristics. Results indicate that the ash fractions in the Nigerian woods were low in K, Si, and Ca, resulting in low calculated alkali indices, hence these fuels are not predicted to cause severe fouling problems. Furthermore, the analysis of the evolved product during devolatilisation from Py-GC-MS suggests that the content of oil is high in Gmelina. Finally, the results from the single particle combustion experiments revealed a longer char burn out rate for Lophira and Nauclea when compared with those of Terminalia and Gmelina.