Low-molecular-weight organic gelators generate physical gels by the formation of three-dimensional fibrous network structures as a response to various physicochemical stimuli such as heat, light, ultrasound and chemical environments. Dibenzylidene sorbitol (DBS) represents a typical compound able to generate gels because of some prerequisite structural features: the presence of functional groups to form intermolecular hydrogen bonds and of aromatic groups to be involved in p-p interactions, or chirality. Herein, we present the synthesis of three derivatives of DBS-bearing carboxy groups attached to phenyl rings and the corresponding spin-labelled compounds. We studied the formation of physical gels resulting from self-assembly of DBS derivatives with the aim of highlighting the influence of the position of the carboxy group on the gel properties. These types of compounds can form gels in polar solvents (such as water, DMSO) by either temperature treatment or variation of the pH. In this study, the systems were investigated by rheological measurements, SEM analysis and EPR measurements. The results showed that the introduction of carboxy groups into the structure of DBS generates weaker gels compared with the parent gelator, DBS. The spin probes used in this study (spinlabelled DBS derivatives and 5-doxyl stearic acid) demonstrated that assembly of gelator molecules is a highly selective process. The two-component feature of EPR