In recent years, several secondary plant metabolites have been identified that possess antimethanogenic properties. Tannin-rich forages have the potential to reduce methane emissions in ruminants while also increasing their nutrient use efficiency and promoting overall animal health. However, results have been highly inconclusive to date, with their antimethanogenic potential and effects on both animal performance and nutrition being highly variable even within a plant species. This variability is attributed to the structural characteristics of the tannins, many of which have been linked to an increased antimethanogenic potential. However, these characteristics are seldom considered in ruminant nutrition studies—often because the analytical techniques are inadequate to identify tannin structure and the focus is mostly on total tannin concentrations. Hence, in this article, we (i) review previous research that illustrate the variability of the antimethanogenic potential of forages; (ii) identify the source of inconsistencies behind these results; and (iii) discuss how these could be optimized to generate comparable and repeatable results. By adhering to this roadmap, we propose that there are clear links between plant metabolome and physiology and their antimethanogenic potential that can be established with the ultimate goal of improving the sustainable intensification of livestock.