One hundred and fifty-six magetic hyperfine transitions belonging to four rotational transitions of the NO-HF complex have been observed using a Fourier transform microwave spectrometer. The magnetic hyperfine structure shows interactions due to the nitrogen, hydrogen, and fluorine nuclei. Analysis of both the fine and hyperfine structure gives a bent geometry with an a axis-NO angle of about 44 degrees and indicates a strong stabilization of the in plane NO pi* orbital with respect to the out of plane orbital. The Fermi contact interactions at the H and F nuclei have the opposite sign and comparison with ab initio calculations suggests assigning the larger positive interaction to the F nucleus. The results reveal details of the distortions of the electronic structure of the partners in the complex caused by the hydrogen bond.