Abstract The 1H NMR spectrum of naphtho [1′,2′:4,5]thieno[2,3‐c]quinoline is highly congested because all the protons are in an aromatic environment, and the structure of the molecule is nearly symmetric. With this in mind, the assignment of the 1H and 13C NMR spectra of this compound obtained using two‐dimensional NMR spectroscopy is reported.