Although phosphonous acid ligands have recently become of interest for use in transition metal complex catalysts for organic reactions such as alkene hydroformylations, the factors that affect the steric and electronic properties of these ligands have not been studied in detail. To gain insight into the electronic and steric properties of phosphonous acid ligands, we have prepared tungsten(0) pentacarbonyl complexes with chlorophosphite ligands derived from either 2,2′‐biphenol or (±)‐1,1′‐bi‐2‐naphthol and have then hydrolyzed the coordinated ligands to generate tungsten(0) pentacarbonyl complexes with the corresponding phosphonous acid ligands. NMR measurements of the W–P coupling constants demonstrate that changing the biaryl groups from biphenyl to binaphthyl does not affect the electron‐donor ability of the ligand, whereas changing the third substituent from chloro to oxo has a significant effect. Estimation of cone angles of the ligands from X‐ray crystallographic data have shown that neither changing the biaryl group nor changing the third substituent have a significant effect on their cone angles. Further, these studies have identified important intra‐ and intermolecular interactions that favor certain ligand conformations. The data could be useful for the development of catalytic structure–activity relationships that could be used in the rational design of catalysts.