The valorisation of clean biogas (CH4/CO2 = 60/40 v/v) by steam reforming over metal open-cell foam-based structured catalysts was investigated. NiCrAl foams were coated by RuMgAl or RhMgAl hydrotalcite-type compounds through electrodeposition to obtain, after calcination, a thin and stable catalytic film of oxides. The active sites for the reforming reactions are highly dispersed Rh or Ru nanoparticles stabilized by a strong metal support interaction, large Ni particles segregated from the support during reduction and reaction, and Rh/Ni bimetallic particles formed by the interaction of the two formers. Rh-based catalysts show superior activity and stability with the time on stream than Ru catalysts, and a low carbon deposition, which is mainly ascribable to the presence of large Ni particles. In comparison to a pelletized catalyst, the structured catalysts are allowed to operate at high space velocities and low Steam to CH4 ratio, increasing the biogas valorisation and thus the productivity.