PNP pincer ligands stabilise diamagnetic base metal catalysts, and much effort has been invested in the development of chiral analogues for asymmetric catalysis. Starting from the conformational issues that affect P-stereogenic diphosphines, we extend the analysis to our recently prepared P-stereogenic PNP pincer ligands, which we used in the iron(ii)-catalysed hydrogenation of ketones. Backbone rigidity and size (and shape) of the substituents at phosphorus are pivotal in both bi- and tridentate P-stereogenic ligands, and their interplay is discussed, as well as the contribution (and shortcomings) of DFT calculations to the understanding of the conformational flexibility and enantiodiscrimination.