The increasing miniaturization of devices creates the need for adequate power sources and direct methanol fuel cells (DMFC) are a strong option in the various possibilities under current development. DMFC catalysts are mostly based on platinum, for its outperformance in three key areas (activity, selectivity and stability) within methanol oxidation framework. However, platinum poisoning with products of methanol oxidation led to the use of alloys. Ruthenium–platinum alloys are preferred catalysts active phases for methanol oxidation from an industrial point of view and, indeed, ruthenium itself is a viable catalyst for this reaction. In addition, the route of methanol decomposition is crucial in the goal of producing H₂ from water reaction with methanol. However, the reaction pathway remains elusive and new approaches, namely in computational methods, have been ensued to determine it. This article reviews the various recent theoretical approaches for determining the pathway of methanol decomposition, and systematizes their validation with experimental data, within methodological context.