The increasing demands for oil and gas and associated difficult drilling operations require oil-based drilling fluids that possess excellent rheological properties and thermal stability. The objective of the present work was to investigate the rheological properties and thermal stability of organo-montmorillonite (OMnt) modified with various surfactants and under various loading levels in oil-based drilling fluids, as revealed by the interaction between organic surfactants and montmorillonite. The influence of the structural arrangement of surfactants on the thermal stability of organo-montmorillonite (OMnt) in oil-based drilling fluids was also addressed. OMnt samples were prepared in aqueous solution using surfactants possessing either a single long alkyl chain two long alkyl chains. OMnt samples were characterized by X-ray diffraction, high-resolution transmission electron microscopy, thermal analysis, and X-ray photoelectron spectroscopy. Organic surfactants interacted with montmorillonite by electrostatic attraction. The arrangements of organic surfactants depended on the number of long alkyl chains and the geometrical shape of organic cations. In addition to the thermal stability of surfactants, intermolecular interaction also improved the thermal stability of OMnt/oil fluids. A tight paraffin-type bilayer arrangement contributed to the excellent rheological properties and thermal stability of OMnt/oil fluids. The deterioration of rheological properties of OMnt/oil fluids at temperatures up to 200°C was due mainly to the release of interlayer surfactants into the oil.