In this work, we report a first detailed study of the mesophasic behaviour of the calamitic liquid crystal, a (4,4′-bis(4″-carboxybelzyloxy)biphenyl derivate, labelled 9/2 RS/RS, showing an isotropic-isotropic-(columnar)-cubic phase behaviour on cooling. ¹H NMR diffusometry allowed to distinguish between the two isotropic phases in terms of diffusion characterized by different Arrhenius activation energy, while ¹³C NMR static measurements and ²H NMR investigations were of help in understanding the orientational ordering properties of the metastable columnar phase and confirmed the isotropic state of the sample in the cubic phase.