This paper describes the use of microcontactprinting (μCP) to form micrometer-scale patterns of copper on poly(tetrafluoroethylene) (PTFE), and illustrates the use of these patterned surfaces as substrates for electrodeposition of polypyrrole (PPy) sensor structures. A patterned elastomeric stamp was used to deliver a nitrogen-containing silane coupling agent to the argon plasma-pretreated PTFE surface. The surface was subsequently activated by PdCl2, allowing the selective activation via the formation of Pd–N complex. Patterning of copper structures with feature sizes of 50–200 μm was achieved by immersing the activated surface into an electroless copper plating bath. Surface chemistry was investigated after each surface modification and deposition step using X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (TOF-SIMS). This study demonstrates a soft lithography approach for the fabrication of patterned copper and PPy structures on flexible PTFE films, offering new opportunities for the creation of polymer-based electronic devices and sensor arrays.