In this study, graphene oxide nanoribbons (GONRs) were synthesized from the facile unzipping of multiwalled carbon nanotubes (MWCNTs) with the help of microwave energy. A core-shell MWCNT/GONR-modified glassy carbon (MWCNT/GONR/GC) electrode was used to electrochemically detect ascorbic acid (AA), dopamine (DA), and uric acid (UA). In cyclic voltammograms, the MWCNT/GONR/GC electrode was found to outperform the MWCNT- and graphene-modified GC electrodes in terms of peak current. For the simultaneous sensing of three analytes, well-separated voltammetric peaks were obtained using a MWCNT/GONR/GC electrode in differential pulse voltammetry measurements. The corresponding peak separations were 229.9 mV (AA to DA), 126.7 mV (DA to UA), and 356.6 mV (AA to UA). This excellent electrochemical performance can be attributed to the unique electronic structure of MWCNTs/GONRs: a high density of unoccupied electronic states above the Fermi level and enriched oxygen-based functionality at the edge of the graphene-like structures, as revealed by X-ray absorption near-edge structure spectroscopy, obtained using scanning transmission X-ray microscopy.