Graphene and graphitic nanoribbons possess different types of carbon hybridizations exhibiting different chemical activity. In particular, the basal plane of the honeycomb lattice of nanoribbons consisting of sp(2)-hybridized carbon atoms is chemically inert. Interestingly, their bare edges could be more reactive as a result of the presence of extra unpaired electrons, and for multilayer graphene nanoribbons, the presence of terraces and ripples could introduce additional chemical activity. In this study, a remarkable irreversibility in adsorption of CO2 and H2O on graphitic nanoribbons was observed at ambient temperature, which is distinctly different from the behavior of nanoporous carbon and carbon blacks. We also noted that N-2 molecules strongly interact with the basal planes at 77 K in comparison with edges. The irreversible adsorptions of both CO2 and H2O are due to the large number of sp(3)-hybridized carbon atoms located at the edges. The observed irreversible adsorptivity of the edge surfaces of graphitic nanoribbons for CO2 and H2O indicates a high potential in the fabrication of novel types of catalysts and highly selective gas sensors.