Poly(butylene succinate) (PBS) nanocomposite structure was studied as a function of the filler percentage loading. The resulting state of dispersion was evaluated by XRD and TEM, and the interfacial attrition between PBS chain and lamellar platelets by the melt rheological properties. Hybrid organic inorganic (O/I) layered double hydroxide (LDH) organo-modified by oleate anions was used as filler. It was found that the confinement supplied by the LDH framework forces the interleaved organic molecule to be more distant from each other than in the case of oleate salt, this having as an effect to decrease strongly the homonuclear intermolecular 1H1H dipolar interaction. An additional consequence of this relatively free molecular rotation, affecting the 13C CPMAS response as well, is to facilitate the delamination of the 2D-stacked layers during extrusion since an quasi-exfoliated PBS:Mg2Al/oleate structure is observed for filler loading lower than 5% w/w. This is in association to a non-linear viscoelasticity in the low-ω region and the observed shear-thinning tendency compares better than other PBS:silicate nanocomposite derivatives and is here explained by the presence of a percolated LDH nanoparticle network. Indeed the plastic deformation in the low-ω region is found to be restricted by well-dispersed LDH tactoids in association with a rather strong attrition phenomenon between tethered oleate anions and PBS chains.