A B S T R A C TBrewer's spent grains, major by-products of the beverage industries, were obtained from a Nigerian brewery and subjected to pyrolysis at 500°C. Analytical pyrolysis (Py-GC/MS) was conducted on the original BSG, extractivefree BSG and BSG CH 2 Cl 2 extract. There was a marked difference in the concentration of levoglucosan between the extractive-free BSG (40.5%) and the original BSG (11.5%). The Py-GC/MS detected significant amount of palmitic and oleic acids in the three samples. Prior to pyrolysis, the extractives content were isolated through methanolysis, transesterified and subjected to GC/MS analysis. The analysis revealed the presence of linoleic, oleic and palmitic acids in an appreciable quantity. The BSG and its biochar were also characterised according to Fourier transform infrared and Raman spectroscopic, and thermogravimetric analyses alongside some conventional physico-chemical analysis. The total crystallinity and condensation indices were evaluated from specific FTIR spectra peaks so as to monitor structural transformations in the bio-char. Kinetic data were deduced from TGA measurements and it was apparent that thermal decomposition of BSG is better modelled as a multi-step reaction mechanism. The nitrogen content of the bio-char was relatively high making it a suitable feedstock for the production of in situ nitrogenised activated bio-carbon. There was a significant variation between the structural configuration of the original BSG and the bio-char as revealed by the change in the value of the condensation index as well as the cellulose crystallinity content. It may thus be concluded that the BSG biomass would be a viable feedstock for thermal decomposition and other valorisation processes.