Maximizing the efficiency and economic benefits of bio-oil is a major challenge for the emerging bio-refining industry. This research has developed a promising route to produce clean-fuel hydrogen with high value carbon nanotubes (CNTs) as a by-product of the process via evaporation/pyrolysis-reforming of crude bio-oil. Since the waste catalyst coke is replaced by high-value CNTs, a potential significant increase of additional economic benefit could be contributed to the bio-refining process. Moreover, CO2 emission to the environment from the current practice of coke oxidation during catalyst regeneration would be reduced.