Octadecylamine (ODA) was used to intercalate a fine-grained and a coarse-grained fraction of natural Mg-vermiculite (VER) using a low-temperature melting procedure. Mixtures of Mg-vermiculite fractions and powdered ODA in the molar ratios of 2:1, 1:1, 1:2 and 1:6 were homogenized and heated for 1, 3, 15 and 30 h at 80°C to prepare intercalated samples. X-ray powder diffraction analysis of intercalated samples was combined with molecular modeling to investigate their interlayer structure. Significant amounts of non-intercalated vermiculite and diffuse peaks with very low intensity and basal spacings close to 29 Å were identified when the lowest concentration (molar ratio VER:ODA = 2:1) was used. According to molecular modeling, this indicates the initial stage of a one-layer arrangement of distorted ODA molecules in the interlayer. If the concentration of ODA molecules and treatment time were increased, a two-layer arrangement of ODA molecules with a different ODA chain-disorder and interlayer-space saturation was identified. Interlayer ODA molecules were inclined to the vermiculite basal plane with an inclination angle for two-layer arrangements that ranged from 76 to 95°. Experimental basal spacings with these two-layer arrangements varied from 52 to 58 Å and were in agreement with molecular modeling results. A fully-saturated 58 Å two-layer ODA arrangement was identified when higher ODA concentrations (VER:ODA = 1:2 and 1:6) and 15 and 30 h treatment times were used. There was no significant difference between ODA-intercalated samples prepared using fine-grained and coarse-grained Mg-vermiculite fractions. A grafted ODA-chain nano-layer with a 49.6(2.1) Å average height was observed on the surface of thin ODA-intercalated micro-flakes using atomic force microscopy. Grafted ODA chains not only created an homogeneous surface nano-layer, but also variable-width channels between the ODA molecules.