The potential use of biomass as energy source in Nigeria is very high and this can be explained from the fact that about 80 % of Nigerians are rural or semi-urban dwellers that depend solely on biomass for their energy source. This research investigates the formulation of bio – coal briquette from groundnut shell, maize cob and rice husk and also studies how incorporation of binder affects the calorific values of the formulated briquettes. Some briquettes were formulated from the agro – waste with the incorporation of equal amounts of starch and coal (samples B, E and H) while in other briquettes, only starch was incorporated (samples A, D and G). Briquette samples C, F and I were formulated without any binder. The result also showed that the briquette samples (with or without binder) has higher burning rate and heating values than firewood. The results showed that all the briquette samples incorporated with starch or starch and coal binders boiled water at 16 min while firewood and briquette samples without binder boiled at 20 min except for maize cob briquette that could not boil water at 20 min. Incorporation of binders was found to increase the calorific values the briquette significantly. It was observed that incorporation of coal as binder had a significant effect only on the calorific value groundnut shell briquette samples. The result showed that briquettes will serve as a more effective substitute for firewood as it shows more combustion characteristics over firewood and the raw materials (agro – waste) are readily available.