New organophilic montmorillonites with oligomers of lactic acid and other compounds such as citric acid, stearic acid, maleic anhydride, pentaerythritol and ε-caprolactone were synthesized. They were characterized by Fourier Transform Infrared Spectroscopy (FTIR), X-ray Diffraction (XRD), Thermogravimetric Analysis (TGA), Scanning Electron Microscopy (SEM), elemental analysis and swelling capacity in water. In all tested composites, an increase in the montmorillonite interlayer distance resulting from intercalation of the modifying substance in the montmorillonite was found by means of XRD. Elemental analysis and FTIR showed that all of the tested samples contained an organic segment in the montmorillonite structure. TGA studies revealed that composites modified with lactic acid oligomers, stearic acid or ε-caprolactone had the highest thermal stability. They also exhibited the lowest swelling capacity which was 2–3 times lower than that for unmodified sodium montmorillonite. Some preliminary studies on the mechanical properties of PLA/modified montmorillonite are also presented and discussed.