We demonstrate in this paper that plasma polymer can be advantageously used to provide surfaces with topography and chemical control at the nanoscale. Moreover, this technique was also proved to he of high interest to functionalize atomic force microscopy tips that were used to probe the patterned surfaces in pulsed force mode. This approach allowed demonstration by a direct observation (lithe possibility of generating alternating hydrophilic/hydrophobic surfaces at the nanoscale prepared by DUV laser irradiation. Such a versatile and simple route opens new possibilities in the field of smart surfaces engineering.