In this contribution, the preparation of rod-coil-rod triblock copolymers based on polydimethylsiloxane and polypeptide [poly(gamma-benzyl-L-glutamate)] is reported. Firstly, self-assembly in rod-like structures was demonstrated via polarized optical microscopy and small-angle light scattering. Further structuration details were obtained using X-ray scattering and AFM imaging to establish the formation of a double-hexagonal structure and to accurately define the morphological dimensions of the rodlike structures. The thermal behavior of these structures was investigated using dynamic mechanical analysis and differential scanning calorimetry. We conclude by addressing an unexpected reversible thermal transition within the 130-150 degrees C temperature range and the ensuing associated organizational modifications.