Organogelation is a useful and novel alternative to structure vegetable oils without the use of trans and/or saturated fats, providing useful and novel functional properties not only to food systems, but also to cosmetics, and pharmaceutical products. However, the relationship between the molecular structure of gelator molecules, their gelling capability, and the physical properties of the organogels is still achieved more by serendipity than by a scientific approach. The 12-hydroxystearic acid (12-HSA) is a well-known gelator molecule that provides a structural platform from which a variety of derivatives can be made easily. In this chapter we discuss the relationship between the molecular structure of 12-HSA, ammonium chloride salts of amines, primary and secondary amides derived from the R enantiopure form of the 12-HSA, with the thermomechanical properties of the organogels developed using vegetable oils as the liquid apolar phase. The chapter discusses results obtained with organogels developed by these gelator molecules under static conditions, and organogels formed under the independent and combined effect of shearing and cooling rate. We also address the role of polar charges in the molecular self-assembly of ammonium chloride salts of amines derived from 12-HSA.