In this work, we report a new intercalation reaction: three different n-alkylamines (n-butylamine, n-hexylamine and n-octylamine), in vapor phase, were intercalated into non-dispersed vanadium pentoxide xerogel and into this lamellar material homogeneously dispersed in Si–O–Si network (obtained by polycondensation of the silicon alkoxide) interpenetrated with V–O–V and V–OH–V polymeric chains. The reaction with non-dispersed xerogel leads to increase of interlamelar distance for low time of reaction (up to 2 hours) and after 24 hours we observed a new phase. In contrast, for the reaction with xerogel dispersed in silica, it was observed only the increase of the basal distance retaining the original bi-dimensional structure (00l diffractions lines were observed); suggesting that the silica matrix stabilizes the vanadium pentoxide structure as the result of a mutual “solubility” due to cross-linking and entanglement of both components. In addition, for this reaction it was observed a selective amine intercalation. The reactions were monitored using powder X-ray diffraction, Fourier-transform infrared and electronic spectroscopy, electron paramagnetic resonance and scanning electron microscopy.