Bis(triisopropylsilylethynyl) pentacene (TIPS pentacene) is a functionalized pentacene derivative designed to enhance both the solution solubility and solid-state packing of pentacene. In this paper, we report our observations of a solid-state phase transition in TIPS pentacene crystals upon heating or cooling. Evidence from differential scanning calorimetry (DSC), hot-stage optical microscopy, as well as high-temperature X-ray and electron diffraction are presented. A reasonable match with experimental data is obtained with molecular modeling. Our results reveal that the transition is associated with a conformational reorganization of the TIPS side groups, accompanied by a slight decrease in the acene-to-acene spacing and a shift of the overlap between the neighboring pentacene units. The observed cracking should be avoided or minimized in TIPS pentacene-based thin film transistors to maintain their relatively high charge carrier mobility.