The "gold standard" for obtaining accurate equilibrium structures is the so-called semi-experimental (SE) approach, which exploits the structural information contained in rotational constants. Within the SE approach, ground-state rotational constants-accurately obtained from high-resolution spectroscopic studies-are computationally corrected in order to remove vibrational effects. The resulting SE equilibrium rotational constants for a significant set of isotopic species allow for retrieving a unique set of equilibrium bond lengths and angles for the molecule under consideration. However, in some cases, the lack of isotopic substitution hampers or even prevents a rigorous and complete structure determination. In this perspective, we introduce the use of dipolar spin-spin coupling constants as an additional source of structural information in support of the standard SE approach. As a proof-of-concept, we tested this new strategy on some prototypical species, such as water, ammonia, phosphine, and their fluorinated counterparts. Our results indicate that-even when the molecular structure can be obtained from a large set of isotopic rotational constants-the use of dipolar spin-spin coupling constants guarantees a better accuracy and reduces the correlations among the geometrical parameters. Moreover, we point out that our approach offers the possibility to fully derive the molecular structure of PF3, a species for which any isotopic substitution is not possible.