The present paper reports the successful elaboration of exfoliated plasticized starch-based nanobiocomposites. This was made possible by using cationic starch as a new clay organomodifier to better match the polarity of the matrix and thus to facilitate the clay exfoliation process. To demonstrate the efficiency of this new approach, either natural (MMT-Na) or organomodified (OMMT-CS) montmorillonite were incorporated into the starch nanobiocomposites by a melt blending process. The morphological analyses (SAXD and TEM) showed that MMT-Na leads to the formation of intercalated nanobiocomposites. On the contrary, OMMT-CS allowed the elaboration of well-exfoliated nanobiocomposites. Tensile tests performed on the obtained nanobiocomposites showed that exfoliated nanobiocomposites display enhanced mechanical properties compared to those of the intercalated nanobiocomposites and neat matrix. These results clearly highlight the great interest in using OMMT-CS to obtain starch-based nanobiocomposites with improved properties.