Oligomers of triacylglycerols (TAGs) are derived from the self-metathesis of vegetable oils and are sought for a variety of applications, in particular waxes. A series of model dimers and quatrimers of TAGs with controlled structures were synthesized and characterized by H-1 NMR and C-13 NMR. Their thermal stability, crystallization, and melting behavior were investigated using TGA and DSC. The relationship of oligomeric structure to thermal properties was found to adhere well to predictive trends. Although the effect of saturation on the phase behavior was the most dramatic, with differences in crystallization temperature up to 62 degrees C, isomerism and molecular mass were shown to affect crystallization significantly, leading to differences of up to 30 degrees C. The findings of the study show that the thermal parameters of the oligomers can be adjusted in a very broad range by saturation, isomerism, and size, making the development of a large variety of biosourced functional lubricants and waxes possible.