Peatlands are large sources of methane (CH₄), and peat structure controls CH₄ production and emissions. We used X-ray microtomography imaging, complex network theory methods, and pore network modeling to describe the properties of peat macropore networks and the role of macropores in CH₄-related processes. We show that conditions for gas transport and CH₄ production vary with depth and are affected by hysteresis, which may explain the hotspots and episodic spikes in peatland CH₄ emissions.