The phase behaviour of metal carboxylates has been the center of significant research over several decades, mainly because they exhibit several pre-melting phases on heating; some of which are liquid crystalline whilst others are crystal-crystal phases. Since for some compounds smectic C type mesomorphic phases are observed, there is great potential for application in Liquid Crystal Display Devices (LCD). Furthermore, their high stability, low toxicity and relative cheapness indicate that they represent viable alternative to conventional nematic and twisted nematic liquid crystals. Interestingly, though these compounds have been know for decades, there remain some unanswered questions regarding the relationship between their solid state structures and phase behaviours, the role played by molecular packing during melting and the characterization of their phase textures. Hence, in this study, the solid state structure and thermal behaviours of a homologous series of silver(I), sodium(I) and Potassium(I) carboxylates are investigated via via solid state NMR and infrared spectroscopies, X-ray powder diffraction, differential scanning calorimetry and polarizing light microscopy.