AbstractBoron‐based compounds such as frustrated Lewis pairs and borylenes that mimic transition‐metal(TM)‐like reactivity have attracted significant interest in recent years. This work examines the reactivity of boron oxide (B₂O₃) towards dioxygen for methane activation. Density functional theory in combination with orbital analysis were utilized to derive mechanistic pathways for methane‐to‐formaldehyde conversion over B₂O₃ in presence of closed‐shell singlet and triplet O₂. Multiple pathways were screened on the triplet spin state. Best route via the triplet spin state depicts the interaction of B₂O₃ with dioxygen (O¹=O²) and CH₄ at a barrier of 49.8 kcal mol⁻¹, to produce an intermediate having a B−O¹−O²H unit and a free CH₃ radical, which later react together at a barrier of 57.6 kcal mol⁻¹, to finally yield HCHO. In the singlet spin state, a free CH₃ radical does not form instead an intermediate with a B−O¹−O²−CH₃ unit is found after crossing a barrier of 41.1 kcal mol⁻¹, which further undergoes via a relatively lower barrier of 23.4 kcal mol⁻¹ to yield HCHO. Thus, the singlet pathway is energetically preferred over the triplet one. Orbitals further capture that at singlet and triplet states, methane activation follows a hydride and a hydrogen‐atom‐transfer mechanism, respectively.