Montmorillonite (MMT) was organically modified with tributyl citrate (TBC). Organoclays (OMMTs) were processed with diisononyl phthalate (DINP)-plasticized polyvinyl chloride (PVC) to form polymer nanocomposites. The produced composite materials showed a contradictory change in properties to that expected of a layered silicate nanocomposite, with a decreased E-modulus and increased gas permeability compared with a material without OMMT. It was experimentally shown that the TBC modifier was extracted from the OMMT and was dispersed in the PVC/DINP matrix, whereupon the OMMT collapsed and formed micrometer-sized agglomerates. Further investigation revealed that TBC has a significant effect on the gas permeability and the E-modulus, even at low additions to a DINP-plasticized PVC. A PVC nanocomposite with the TBC acting as both the OM for MMT and as the primary plasticizer was produced. This material showed a significantly increased E-modulus as well as a decrease in gas permeability, confirming that it is possible to develop a nanocomposite based on plasticized PVC, if both the organo-modification of the MMT and the formulation of the matrix are carefully selected.