With the emergence of hydrophobic deep eutectic solvents (DESs), the scope of applications of DESs has been expanded to include situations in which miscibility with water is undesirable. Whereas most studies have focused on the applications of hydrophobic DESs from a practical standpoint, few theoretical works exist that investigate the structural and thermodynamic properties at the nanoscale. In this study, Molecular Dynamics (MD) simulations have been performed to model DESs composed of tetraalkylammonium chloride hydrogen bond acceptor and decanoic acid hydrogen bond donor (HBD) at a molar ratio of 1:2, with three different cation chain lengths (4, 7, and 8). After fine-tuning force field parameters, densities, viscosities, self-diffusivities, and ionic conductivities of the DESs were computed over a wide temperature range. The liquid structure was examined using radial distribution functions (RDFs) and hydrogen bond analysis. The MD simulations reproduced the experimental density and viscosity data from the literature reasonably well and were used to predict diffusivities and ionic conductivities, for which experimental data are scarce or unavailable. It was found that although an increase in the cation chain length considerably affected the density and transport properties of the DESs (i.e., yielding smaller densities and slower dynamics), no significant influence was observed on the RDFs and the hydrogen bonds. The self-diffusivities showed the following order for the mobility of the various components: HBD > anion > cation. Strong hydrogen bonds between the hydroxyl and carbonyl groups of decanoic acid and between the hydroxyl group of decanoic acid and chloride were observed to dominate the intermolecular interactions.