Gels of edible oils, also called oleogels, are developed as alternative products of solid fats to limit the uptake of saturated and trans-unsaturated fats and lower the associated risk of coronary disease. The gelation of oils can be achieved with a low molecular weight organogelator (LMWO), a compound that self-assembles at low concentrations in a solid 3D network and provides the mixture its solid-like behavior. We have studied N-palmitoyl-L-phenylalanine (Palm-Phe), an endogenous compound (i.e. naturally present in the human body) as a model LMWO of rapeseed oil. Palm-Phe forms gels at a concentration of 1 wt% in rapeseed oil. We have studied the thermodynamic and mechanical behavior of the corresponding gels. As evidenced by DSC and rheology, this system exhibits two transitions upon heating, in addition to the sol-gel transition, a gel-gel transition between two polymorphic gels. The structural differences between both polymorphs were revealed using cryo-SEM, X-rays scattering, and FTIR experiments. The metastability of one of the polymorphs was proven by ageing and annealing experiments.