Polymeric gel electrolyte systems have gained great interest in the last few years due to their suitability for the manufacturing of ionic devices, for example, for dye-sensitized solar cells (DSSCs). In this work, the rheological behavior at fixed temperatures and at fixed frequency of complex systems based on polyacrylonitrile (PAN) and plasticizers such as ethylene carbonate (EC) and propylene carbonate (PC) containing tetrahexylammonium (Hex(4)NI) and magnesium iodide (MgI2) was studied. These results for these PAN-EC-PC gels suggest a structural change of the "strong-to-weak" type at about 60 A degrees C and the beginning of the gel-sol transition at about 75 A degrees C. These transitions occur at higher temperatures for polymer electrolyte gels containing Hex(4)NI and even higher with MgI2, suggesting the possibility of post-factum treatments of the gels and of the DSSCs to improve their performance. The rheological results suggest that the progressive substitution of Hex(4)NI with MgI(2)leads to a significant improvement in the rheological behavior of the PAN-based electrolytic gel due to the decrease of the mobility of the macromolecules and probably to an increase of the interaction between the inorganic ions and the macromolecules. Moreover, when these gels were used in DSSCs, the sample containing 80(Hex(4)NI)/40(MgI2) showed the best performance considering its rheological and calorimetric behavior as well as energy conversation efficiency and short-circuit current density.