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The design and tuning of new ligands is crucial for unlocking new reactivity at transition metal centers. Azophosphines have recently emerged as a new class of 1,3-P,N ligands in ruthenium piano-stool complexes. This work shows that the azophosphine synthesis can tolerate N-aryl substituents with strongly electron-donating and electron-withdrawing para-R groups and that the nature of this R group can affect the spectroscopic and structural properties of the azophosphines, as measured by NMR spectroscopy, UV–vis spectroscopy, single-crystal X-ray diffraction, and DFT studies. Azophosphines are shown to be relatively weak phosphine donors, as shown by analysis of the 1JP–Secoupling constants of the corresponding azophosphine selenides, but the donor properties can be fine tuned within this area of chemical space. Monodentate and bidentate Ru–azophosphine complexes were prepared, and their first use as a catalyst was probed. The Ru–azophosphine complexes were found to promote the transfer hydrogenation of acetophenone to 1-phenylethanol without the requirement of a harsh base additive, and the bidentate complex was more active than the monodentate analogue.