In this study, a thermodynamic analysis is conducted to investigate the chemical effect, in terms of intrinsic contact angle (CA), on the superhydrophobic behavior. It is theoretically revealed that the essential effect of intrinsic CA is to promote the composite transition. In particular, a large intrinsic CA more than 90° is necessary for such transition. Furthermore, for a pillar system with an intrinsic CA smaller than 90°, composite states are not impossible but is thermodynamically unstable. Once composite states are achieved, the advancing or maximum CA always approaches 180° whether an intrinsic CA is larger or smaller than 90°. In addition, the role of intrinsic CA in the water-repellent or self-cleaning behavior such as contact angle hysteresis (CAH) and equilibrium CA has been discussed in detail.