Surface sizing is employed to increase the wetting resistance against liquids and to improve strength and surface properties of paper. Starch solution is the most widely used for surface sizing, and its effect is highly dependent upon how deep the starch solution penetrates into the paper structure. Better tensile strength can be obtained when starch penetrates deep into the thickness direction of paper. However, holdout of starch solution is beneficial for improving the stiffness and air or liquid resistance. This study was focused on the use of cationic polyacrylamide (PAM) as a surface sizing additive to control the penetration of starch solutions into paper, thus improving bending stiffness of paper. The effects of the ionic property, viscosity, and charge density of PAM on starch penetration and bending stiffness of surface sized papers were investigated. The penetration of starch solution was investigated with confocal laser scanning microscopy. The enthalpy changes accompanying the mixing of cationic PAMs with oxidized starch was determined using an isothermal titration calorimeter to see the molecular level interaction between PAM and starch in mixing. The addition of cationic PAM to oxidized starch solution made starch molecules stay on the paper surface rather than penetrating into the paper structure.