<p>It is well known that colonic microbiota is influenced by both intrinsic and extrinsic factors; out of all these, diet plays a major role. The traditional human diet has typically been high in overall dietary fiber intake, due its inherent presence in plant-derived foods. However, over the years, dietary patterns have transitioned into a low-fiber Westernized diet. This diet is increasingly implicated in colonic diseases. Dietary fiber consumption is known to increase microbial diversity, yet the mechanisms are still unclear. This is partially true because dietary fiber as a category is composed of a wide variety of structures, which may have divergent effects on the gut microbiome. The food industry has extracted, isolated, refined and purified non-digestible carbohydrates and, in some cases, modified them for improved function, which may influence their interaction with the gut microbiome. This study was developed in two phases: we first hypothesized that glucans produced by different processes were structurally distinct and that these fine structural differences in glucans would govern microbial responses to the polymers. To test this hypothesis, we first determined the structural characteristics of the glucans by gas chromatography and mass spectrometry, which revealed substantial structural differences among the glucans with respect to size and linkage patterns, consequently categorizing the glucans by structure (i.e., mixed linkage α-glucans, resistant maltodextrins, and polydextroses). The second study involved the <i>in vitro </i>fecal fermentation of these commercially available soluble glucans which are uniformly composed of glucose linked into different structural arrangements. We further hypothesized that each glucan would select for different microbiota and that there would be glucan-specific general responses across microbiomes. We were able to identify a variety of idiosyncratic metabolic patterns as well as differential organisms selecting for specific glucan structures. Although there were associations with glucan classes at the family level (e.g., <i>Bacteriodaceae </i>and <i>Lachnospiraceae </i>were discriminants of the resistant maltodextrins and polydextroses respectively), associations with glucans across individual species within these families varied. These findings suggest that microbiome responses to structurally distinct glucans depend upon both fine glucan structure and community context, and community metabolic phenotypes emerge from the interaction of the two. These findings are relevant to the food industry as they may enable optimization of synthesis to generate chemical structures that select for specific organisms and/or improve overall gut health.</p>