The on-surface ligation of nitric oxide (NO) with Co-tetraphenylporphyrin (CoTPP) sublimed onto oxygen-reconstructed Ni(001) is studied using room-temperature scanning tunneling microscopy (STM) and complementary photoemission spectroscopies. On the oxygen-reconstructed substrates, the porphyrins are observed to form well-ordered, self-assembled layers. STM directly images the NO ligand as a characteristic feature in the center of the molecule. Under certain STM imaging conditions the dynamicity of this feature can be related to the temperature-activated conformational flexibility of the NO ligand. This provides an indirect confirmation of the bending of the Co-NO bond, as predicted from classical coordination chemistry.