Abstract The dependency of substrate roughness on wetting properties of self‐assembled monolayers (SAMs) has been studied extensively, but most previous studies used limited selection of probing liquid and range of surface roughness. These studies disregarded the limit to observation of sub‐nanometer odd–even parity effect, hence are inconclusive. In this work we report the role of solvent polarity on the roughness‐dependency of wetting behavior of SAMs by studying static con‐tact angle of a variety of probing liquids, with different polarities, on SAMs formed on Ag‐based substrate with different surface morphology. By overlapping the roughness ranges with previous studies on Au, the limitation of surface roughness (RMS=1 nm) to observation of the odd–even effect using water as probing liquid was confirmed, but other probing liquid yielded different roughness‐dependent behaviors, with more polar solvent showing more roughness‐dependent behavior. Based on these observations, we concluded that there exists a phase‐transition like behavior in SAMs due to substrate roughness and molecule chain length, but whose determination is dependent on the probing liquid.