The unzipping of temperature-induced multi-walled carbon nanotubes (MWCNTs) to yield graphene nanoribbons (GNRs) has been studied. These carbon nanomaterials consisting of MWCNTs and unzipped MWCNTs have been synthesized, thoroughly characterized, and subsequently evaluated for electrochemical sensing. Three temperatures (55, 65 and 75 ºC) yielding three carbon nanomaterial termed as GNR-55, GNR-65 and GNR-75, respectively, were carefully studied. Interestingly, GNR-65 became the most suitable material for the electrochemical sensing of a wide range of model analytes displaying the best electrochemical response with independence of the analysed molecule. This electrochemical behaviour seems to be associated to the progress of the unzipping reaction that influences the balance between the Csp2/Csp3 ratio, the graphitic fraction and the type of functional groups introduced. These results revealed the importance of the temperature in the synthesis process, for tailoring carbon nanomaterials which could be used in a particular molecular detection application opening new opportunities for electrochemical sensing applications. ; This work has been Financial supported by the Spanish Ministry of Science and Innovation (CTQ2011-28135), the NANOAVANSENS program from the Community of Madrid (S2013/MIT-3029), the Spanish MINECO (ENE2013-48816-C5-5-R), the Government Aragon (Project DGA_ESF-T66 CNN) and the European Social Fund (ESF). D. A. M. acknowledges the FPU fellowship from the Ministry of Education, Culture and Sports. D. M. M.-G. acknowledges the fellowship received from the NANOAVANSENS program. ; Peer reviewed