Lignin syringyl to guaiacyl ratio (S/G) has long been suspected to have measurable impacts on biochar formation, but these effects are challenging to observe in biochars formed from whole biomass. When the model bioenergy feedstock Populus trichocarpa (cottonwood), with predictable lignin macromolecular structure tied to genetic variation, is used as feedstock for biochar production, these effects become visible. In this work, two P. trichocarpa variants having lignin S/G of 1.67 and 3.88 were ground and pyrolyzed at 700 °C. Water-demineralization of feedstock was used to simultaneously evaluate any synergistic influences of S/G and naturally-occurring potassium on biochar physicochemical properties and performance. The strongest effects of lignin S/G were observed on specific surface area (S) and oxygen-content, with S/G of 1.67 improving S by 11% and S/G of 3.88 increasing total oxygen content in demineralized biochars. Functional performance was evaluated by breakthrough testing in 1% NH. Breakthrough times for biochars were nearly double that of a highly microporous activated carbon reference material, and biochar with S/G of 3.88 had 10% longer breakthrough time than its lower S/G corollary. Results support a combination of pore structure and oxygen-functionalities in controlling ammonia breakthrough for biochar.