Synthesis of the all-silica Deca-Dodecasil 3 Rhombohedral (DD3R) zeolite was accelerated 10 times by seeding with small amount of crystals (0.02 wt%) with yields approaching 100%. The effects of other synthesis variables, like silica source, the presence of methanol or the synthesis pH on the final product distribution have been studied. The adsorption and separation of propylene and propane mixtures on this material are presented. The improved synthesis may form the basis to scale-up production of DD3R for selective separation processes. The single component adsorption isotherms could be well described with a dual-site Langmuir model. The binary mixture adsorption was determined from breakthrough/desorption experiments at 323, 358 and 383 K. By modelling the adsorptive column, diffusion coefficients at infinite dilution for single component and the effect of propane over propylene adsorption were determined. Cylindrical geometry describes the pore topology of DDR type materials well. Propane decreases the uptake rate of propylene by adsorption in the surface of the crystals. Propylene diffusion is best described by the “strong confinement” model inside the zeolite cages. Separation is due to only propylene adsorption with diffusion as rate determining step.