In preparation of self-repairing polymer-modified waterproofing asphalt-montmorillonite (MMT) composite, silylation-modification charcteristics of cation (Na+) exchanged K-10 (Na-MMT-K) using 3-aminopropyltriethoxysilane (APS) were studied and the optimal conditions of its silylation-modification process were proposed by use of the results of instrumental analysis, including FTIR, XRD, NMR and TGA, on silylation-modified Na-MMT-K (S-Na-MMT-K) under various conditions. According to FTIR analysis on S-Na-MMT-K, its peak-strengths of Si-O, -NH2, -CH2- and -OH, correlated with APS silylation-modification reaction, were compared each other. As a result, its optimal conditions including APS-MMT reacting period, APS-stirring period prior to APS-MMT reaction, APS concentration and reaction temperature were turned out to be 2~3 h, 20 min, 7.5 w/v% and 50 °C, respectively. In addition, the optimal conditions induced from the results of TGA were also nearly consistent to those according to the results of FTIR analyses. These optimal conditions were turned out to be almost consistent to those drawn according to a criterion from XRD results suggested previously by Lee et al., by which the criterion was validated.