A multinuclear solid state NMR approach is applied to four templated mesoporous oxides (silica, titania, niobia and tantala) to include 15N and 17O magic angle spinning (MAS) NMR and double resonance 15N-93Nb, 17O Rotational-Echo Adiabatic Passage Double Resonance (REAPDOR). The templated samples were ramped in steps of 20 °C for 2 days up to typically 110 °C where the samples were left for 2-4 days. 15N MAS NMR shows that amines are the only species present in the TiO2, Nb2O5, and Ta2O5. In SiO2, amines are only present as a minor coordination (10 ( 2%), but there are several strong ammonium 15N resonances. The REAPDOR experiments show that the nitrogen interacts with niobium, confirming a ligand interaction between the Nb and N, as previously believed. In the case of silica, the amine is quaternized and there is apparently no interaction with the Si, suggesting a RNH3 + -O-Si- hydrogen-bonding interaction with the walls. 17O MAS NMR provides the clearest indication of the local wall structure. In the aged, templated samples in all cases only OM2 coordinations are present which is very different from the pure bulk oxides (apart from SiO2) and must be due to the effects of amine coordination at the metal centers. On removal of the template, these oxides behave differently, with Ta2O5 showing a mixture of OTa2 (85 ( 5%) and OTa3 (15 ( 5%) which is similar to the types of coordination found in the bulk oxide. The previously reported 17O MAS NMR data from heat-treated mesoporous niobia shows only ONb2, which is very highly ordered. In contrast for titania, the OTi2 coordination is immediately lost on removal of the template to be replaced by a mixture of OTi3 (60 ( 5%) and OTi4 (40 ( 5%), with the OTi4 becoming dominant above 250 °C, very different behavior from the corresponding bulk oxide. In summary, this NMR study shows that the local oxygen coordination in amine-templated mesoporous transition metal oxides is present as OM2 which is relatively rare in bulk oxides. The data indicates that the template interaction is largely controlled by the N-M dative bond to the wall, suppressing higher oxygen coordination numbers. Qualitatively it appears that the strength of this interaction varies greatly in the different mesoporous oxides.