Montmorillonite (MMT) and multi-walled carbon nanotube (MWCNT) are presently the leading and most effective studied nanofillers reported to impact high properties in various polymeric matrices. Meanwhile, the main challenge in nanocomposite is achieving efficient dispersion of these nanoparticles without agglomeration in the selected matrix. In this study, we investigated the influence of various types of montmorillonite and carbon nanotubes in determining the most stable MMT/MWCNT hybrid formulation, and the optimum mixing ratio of the two fillers was selected to prepare MMT/MWCNT hybrid via lyophilization process. Three kinds of nanoclays (Cloisite MMT Na+, MMT 10A and MMT 20A) and two types of MWCNT (pristine MWCNT and functionalized MWCNT "MWCNT-f") have been investigated. The most stable and optimum MMT/MWCNT hybrid was incorporated into poly(lactic acid) (PLA) matrix. The various characterization results revealed the success of the lyophilization procedure, and that the prepared MMT/MWCNT hybrid influenced high properties in the nanocomposites.