NiMoS₂ nanoparticles supported on carbon, synthesized by a microemulsion method were used as a nanocatalyst for hydrodeoxygenation (HDO) of a lignin model compound – guaiacol. Two types of carbon supports – mesoporous carbon (CMK-3) and activated carbon (AC) with a predominantly microporous structure, were studied to investigate the role of porosity and nature of the porous structure in catalyst activity. The activity of NiMoS₂/AC resulted in the complete guaiacol conversion at 13 h of reaction time to produce phenol (31.5 mol%) and cyclohexane (35.7 mol%) as the two main products. Contrastingly, NiMoS₂/CMK-3 needed a much lesser reaction time (6 h) to attain a similar conversion of guaiacol but gave different selectivities of phenol (25 mol%) and cyclohexane (55.5 mol%). Increased cyclohexane production with NiMoS₂/CMK-3 implied better deoxygenation of MoS₂ and enhanced hydrogenation capacity of Ni since phenol is a partially deoxygenated product of guaiacol while cyclohexane is a completely deoxygenated and hydrogenated product. The superior catalytic activity and deoxygenating behavior of NiMoS₂/CMK-3 catalysts could be attributed to the organized mesoporosity of the CMK-3 support in relation to the improved active phase distribution and access to active sites that facilitate the conversion of the reaction's product. Recyclability study implied NiMoS₂/CMK-3 was more stable without significant changes in the catalytic activity even after three reaction cycles.