The present work highlights the progress in the field of polymeric package reliability engineering for a flexible thermoelectric generator realized by thin-film technology on a Kapton substrate. The effects of different plasma treatments on the mechanical performance at the interface of a poly(dimethylsiloxane) (PDMS)/Kapton assembly were investigated. To increase the package mechanical stability of the realized wearable power source, the Kapton surface wettability after plasma exposure was investigated by static contact-angle measurements using deionized water and PDMS as test liquids. In fact, the well-known weak adhesion between PDMS and Kapton can lead to a delamination of the package with an unrecoverable damage of the generator. The plasma effect on the adhesion performances was evaluated by the scratch-test method. The best result was obtained by performing a nitrogen plasma treatment at a radio-frequency power of 20 W and a gas flow of 20 sccm, with a measured critical load of 1.45 N, which is 2.6 times greater than the value measured on an untreated Kapton substrate and 1.9 times greater than the one measured using a commercial primer.