The effect of length scale of tri-block oil soluble polymer (poly (ε-caprolactone)–poly butadienepoly (ε-caprolactone) (PCL-PB-PCL) on the properties of an water-in-oil (W/O) droplet microemulsion (R ~ 5.5 nm) has been studied as a function of the amount of added telechelic polymer. SAXS measurements show that the size of the droplets is not affected by the polymer addition but it induces attractive interactions at low concentration and repulsive ones at high polymer content. Measurements of the diffusion coefficient by dynamic light scattering (DLS) show different relaxation in mixed systems. The fast diffusion coefficient increases with increasing of polymer concentration. At higher polymer content the network formation leads to an additional slow relaxation mode in DLS that can be related to the formation of clusters of microemulsion droplets interconnected by the polymer. The collective diffusion of slow relaxations is decreases with increase of polymer concentrations.

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