This overview of polythiophene-based materials provides a critical examination of meaningful examples of applications of similar electrode materials in electroanalysis. The advantages arising from the use of polythiophene derivatives in such an applicative context is discussed by considering the organic conductive material as such, and as one of the components of hybrid materials. The rationale at the basis of the combination of two or even more individual components into a hybrid material is discussed with reference to the active electrode processes and the consequent possible improvements of the electroanalytical performance. In this respect, study cases are presented considering different analytes chosen among those that are most frequently reported within the classes of organics and inorganics. The use of a polythiophene matrix to stably fix biological elements at the electrode surface for the development of catalytic biosensors and genosensors is also discussed. Finally, a few possible lines along which the next research in the field could be fruitfully pursued are outlined. Furthermore, the work still to be done to exploit the possibilities offered by novel products of organic synthesis, even along paths already traced in other fields of electrochemistry, is discussed.