A novel poly(AM-DMDAAC)/MMT superabsorbent nanocomposites are prepared by radical polymerization using ammonium persulfate (APS) and anhydrous sodium sulfite as a free radical initiator and N,N-methylene bisacrylamide (MBA) as a crosslinker. In this paper, an optimization study on the synthesis of superabsorbent nanocomposites is carried out. Orthogonal array experiment indicates that the optimized conditions is acrylamide (AM) content 23 wt%, diallyl dimethyl ammonium chloride (DMDAAAC) content 6 wt%, montmorillonite (MMT) content 4 wt%, initiator content 0.2 wt% and crosslinker content 0.02 wt%. Under the optimization syntheses conditions concluded, the maximum water absorbency in distilled water is $659.53g{cdot}g^{-1}$ and in 2 wt% sodium chloride solution is $116.25g{cdot}g^{-1}$. Compared with the range values of different factors ($R_j$), the order of significance factors in distilled water is C (MMT) > B (DMDAAC) > A (AM) > D (crosslinker) > E (initiator). MMT is intercalated during polymerization reaction and a nanocomposite structure is formed as shown by TEM analysis and XRD analysis.