Ca-montmorillonites were exchanged with both metal cations (manganese and copper) and organic cations (tetramethylammonium (TMA) and hexadecyltrimethylammonium (HDTMA)) to study the cation size effects on the pore structure and surface roughness of montmorillonite based on the classical and fractal analysis of their nitrogen adsorption isotherms. The surface fractal dimension D was calculated from their nitrogen isotherms with the aid of the recently proposed Neimark equation. The decrease of BET surface area of montmorillonite induced by the larger size of exchange cation was interpreted with both the coverture of some surface roughness (surface screening effect) and the inhibition of nitrogen molecule into some pores (pore blocking effect), The pore blocking effect was examined with the changes of mean pore size. Meanwhile, the D value was used to examine whether or not the surface screening effect existed. It was concluded that the combination of classical and fractal analyses of nitrogen isotherms may facilitate our understanding of the evolution of pore and surface structures of clay exchanged with different cations.