Synthesizing high-value chemicals through C-C coupling of the intermediates from CH4 dissociation is considered as the most promising pathway for efficient utilization of methane as a C-1 resource. Herein, the elementary steps of CH4 dissociation and a possible mechanism for forming C-2 species on the Mo-terminated MoC surfaces were studied using density functional theory (DFT) calculations. Our results indicate that the Mo-terminated MoC surfaces derived from different bulk phases (alpha- and delta-) of MoC possess a similar mechanism to that on the noble-metal surfaces for methane dissociation, i.e., CH4 dissociates sequentially to (CH)(ad) with both kinetic and thermodynamic feasibililies while breaking the last C-H bond in (CH)(ad) is highly activated. As such, C-C coupling through dimerization of the (CH)(ad) species occurs more readily, resulting in (C2H2)(ad) on the Moterminated surfaces. Such (C2H2)(ad) species can dehydrogenate easily to other C-2 adsorbates such as (C2H)(ad) and (C-2)(ad). Consequently, these C-2 species from CH4 dissociation will likely be the precursor for producing long chain hydrocarbons or aromatics on molybdenum carbide based catalysts.