A series of polyimide supramolecular systems containing different amounts of azochromophore were tested as flexible supports that can be used in the fabrication of certain devices, such as sensors for monitoring the temperature changes, by coating them with conductive metals. That is why it is required to have good interfacial compatibility between the flexible substrate and the inorganic layer. The interface of the sensor elements must be designed in such a way as to improve the sensitivity, accuracy, and response time of the device. Laser irradiation is one of the commonly employed techniques used for surface adaptation by patterning polyimides to increase contact and enhance device reliability and signal transmission. In this context, this work highlights unreported aspects arising from the azo-polyimide morphology, local nanomechanical properties and wettability, which are impacting the compatibility with silver. The texture parameters indicate an improvement of the modulations’ quality arising after laser irradiation through the phase mask, increasing the bearing capacity, fluid retention, and surface anisotropy when the amount of the azochromophore increases. The force curve spectroscopy and wettability studies indicated that the modification of the polymer morphology and surface chemistry lead to a better interfacial interaction with the metal lines when the azo component and the polyamidic acid are in equimolar quantities.