The influence of solid–liquid adhesive property on liquid slippage at solid surfaces has been investigated using experiment approach on well-defined model surfaces as well as theoretical analysis. Based on a classical molecular-kinetic description for molecular and hydrodynamic slip, we propose a simple theoretical model that directly relates the liquid slip length to the liquid adhesive force on solid surfaces, which yields an exponential decay function. Well-defined smooth surfaces with varied surface wettability/adhesion are fabricated by forming self-assembled monolayers on gold with different mole ratios of hydrophobic and hydrophilic thiols. The adhesive force of a water droplet and the molecular slippage on these surfaces are probed by surface force apparatus and quartz crystal microbalance measurements, respectively. The experiment results are well consistent with our theoretical prediction. Our finding benefits the understanding of the underlying mechanism of liquid slippage on solid surfaces at molecular level and the rational design of microfluidics with an aim to be frictionless or highly controllable.