Systems with short hydrogen bonds (H-bonds) are notoriously difficult to describe even using cutting edge experimental techniques supported by advanced computational protocols. One of the most challenging issues is the highly dislocated H-bonded proton, which is typically smeared over a large area, featuring complex dynamics governed by pronounced nuclear quantum effects. Thus, in combination with experimental results, these systems offer a rich platform for the benchmarking of various computational approaches and methods. Herein, we present a methodology combining experimental and computational assessment of H-bond observables probed by the nuclear quadrupole resonance technique. Focusing on the case of picolinic acid N-oxide featuring one of the shortest known hydrogen bonds (ROO ∼ 2.425 Å), we compare the predictions of nuclear quadrupole coupling constants (NQCCs) for a series of computational models differing in fine structural details of the H-bond. By comparing the computed 14N and 17O NQCCs with the measured ones and by analyzing the sensitivity of NQCCs to H-bond geometry variations, we demonstrate that NQCCs represent a very sensitive probe for H-bond geometry, particularly the proton location, thereby offering, in conjunction with computations, an accurate and reliable tool for the fine structural characterization of short H-bonds. Importantly, the present methodology is a good compromise between accuracy and computational cost.