Several electronic applications must withstand elevated temperatures during their lifetime. Materials and packages for use in high temperatures have been designed, but they are often very expensive, have limited compatibility with materials, structures, and processing techniques, and are less readily available than traditional materials. Thus, there is an increasing interest in using low-cost polymer materials in high temperature applications. This paper studies the performance and reliability of sensor structures attached with anisotropically conductive adhesive film (ACF) on two different organic printed circuit board (PCB) materials: FR-4 and Rogers. The test samples were aged at 200 °C and 240 °C and monitored electrically during the test. Material characterization techniques were also used to analyze the behavior of the materials. Rogers PCB was observed to be more stable at high temperatures in spite of degradation observed, especially during the first 120 h of aging. The electrical reliability was very good with Rogers. At 200 °C, the failures occurred after 2000 h of testing, and even at 240 °C the interconnections were functional for 400 h. The study indicates that, even though these ACFs were not designed for use in high temperatures, with stable PCB material they are promising interconnection materials at elevated temperatures, especially at 200 °C. However, the fragility of the structure due to material degradation may cause reliability problems in long-term high temperature exposure.