Surface treatment of polydimethylsiloxane (PDMS) with a rotative nozzle atmospheric pressure plasma jet (APPJ) was reported. Operating conditions were optimized by statistical design of experiments, using water contact angle and XPS as response variables; OES (optical emission spectroscopy) was used for plasma diagnosis. The nozzle‐PDMS distance and the torch speed were the most influencing parameters and were optimum at 6.6 mm and 10.3 m s−1, respectively. The extent of hydrophobic recovery of treated PDMS, investigated by water contact angle measurements, was less than what reported in the literature for this amorphous polymer. However, the APPJ treatment proposed in this paper is meant to be inserted in line for a homogeneous surface treatment of PDMS for enhanced adhesion improvement to coatings or adhesives.