To better understand the adsorption of long-chain poly(1 → 4)-β-D-glucans on carbon surfaces as well as interactions responsible for this adsorption, we use a comparative study involving mesoporous carbon-silica composite materials that have been etched to varying degrees and all-atom molecular dynamics simulations. The materials synthesized as part of this etching study consist of an as-synthesized composite material (MCN-MSN), MCN-MSN-0.5 (composite materials consisting of 50% carbon by mass), MCN-MSN-0.3 (composite materials consisting of 70% carbon by mass), and MCN, in which silica etching was conducted using an aqueous ethanolic solution of either NaOH or HF. Data for the adsorption of long-chain glucans to these materials from concentrated aqueous HCl (37 wt %) solution demonstrate a direct relationship between the amount of β-glu adsorption and the magnitude of exposed carbon mesopore surface area, which systematically increases and is also accompanied by an increase in the mesopore size during silica etching. This demonstrates β-glu adsorption as occurring on internal carbon mesopores rather than exclusively on the external carbon surface. These experimental data on adsorption were corroborated by molecular dynamics (MD) simulations of β-glu adsorption to a graphene bilayer separated by a distance of 3.2 nm, chosen to correspond to the carbon mesopore diameter of the experimental system. Simulation results using a variety of β-glu solvent systems demonstrate the rapid adsorption of a β-glu strand on the graphitic carbon surface via axial coupling and are consistent with experimentally observed trends in fast adsorption kinetics. Solvent-mediated effects such as small-scale hydrophobicity and preferential interactions with ions are shown to play important roles in modulating glucan adsorption to carbon surfaces, whereas experimental data on hydrophobically modified silica demonstrate that hydrophobicity in and of itself is insufficient to cause β-glu adsorption from concentrated aqueous HCl solution. (Figure Presented).