In Taiwan, a considerable amount of coffee residue is produced from commercial activities without valuable utilization. To evaluate high-value valorization in the production of highly porous carbon materials, this study investigated the thermochemical properties of coffee residues and further pyrolysis for producing highly porous biochar products at an elevated temperature (i.e., 850 °C) and a moderate residence time of 30 min. Our findings indicate that this biomass has a relatively high calorific value (about 27 MJ/kg, dry basis) due to its low ash and high lignocellulose content. It can be also concluded that the non-activated biochar products are highly porous carbon materials with excellent pore properties (i.e., a BET surface area of about 800 m2/g and a total pore volume of 0.4 cm3/g), which are slightly lower than those of commercial activated carbon products. Based on the above-mentioned results and the high-value circular bio-economy promoted by regulatory policy in Taiwan, the prospects for the possible valorization of coffee residue from commercial shops are addressed here, focusing both on the reuse of plant-based residue (or agricultural waste) as a high-value bioresource in the production of biomass-based fuels and on carbon materials. The former includes solid recovered fuel (SRF) and biomass-to-biogas power. By contrast, the latter aims at the production of plant-based carbon as natural, edible colorants in accordance with the regulation of food safety and sanitation in Taiwan.