Oxygen-17-enriched triphenylphosphine oxide and three of its halogen-bonded cocrystals featuring 1,4-diiodotetrafluorobenzene and 1,3,5-trifluoro-2,4,6-triiodobenzene as halogen bond donors have been characterized by P-31 and O-17 single-crystal NMR spectroscopy. Single-crystal NMR allows for the measurement of not only the magnitudes of various NMR interaction tensors, but also their orientations relative to the crystal lattice and therefore relative to the halogen bonds themselves. P-31 chemical shift tensors, O-17 chemical shift tensors, O-17 quadrupolar coupling tensors, and P-31-O-17 indirect nuclear spin-spin (J) coupling tensors are reported here for P=O center dot center dot center dot I halogen bonds. The angular deviations in the directions of the pseudo-unique components of the P-31 chemical shift tensors, the O-17 chemical shift tensors, and the (17)Oquadrupolar coupling tensors from the direction of the oxygen-iodine halogen bond correlate with the deviations in linearity of the P=O center dot center dot center dot I halogen bond. There is also a clear decrease in anisotropy and an increase in asymmetry of the J( P-31, O-17) coupling tensors attributable to the formation of iodine-oxygen halogen bonds. The small but quantifiable changes in the tensors are consistent with the weak nature of these halogen bonds relative to the P=O motif. Overall, this work establishes single-crystal NMR as a novel probe of halogen bonds in solids. Analysis of the results has provided insights into the correlations between the magnitude and orientation of various NMR interaction tensors and the local geometry of the halogen bond. Gauge-including projector-augmented wave computations corroborate the experimental findings.