The poly[(2-dimethylamino)ethyl methacrylate]-l-polyisobutylene (PDMAEMA-l-PIB) amphiphilic network (APN), a new class of cross-linked systems, was synthesized by the use of methacrylate-telechelic PIE obtained via quasiliving carbocationic polymerization. The swelling dynamics and the free volume changes of this APN was followed by simultaneous swelling and positron annihilation measurements. It was found that the Lifetime of ortho positrons (o-Ps) increases with increasing swelling ratio (R), reaches a maximum at relatively low R, and decreases to a constant value at equilibrium swelling. These findings indicate the collapse of the hydrophobic PIE domains and expansion of the hydrophilic PDMAEMA phase in the net-work upon contacting with water. After reaching the maximum, the decrease of the lifetime parameter is caused by filling the free volume with water in the network. A striking observation was obtained for the o-Ps formation intensity as a function of time (or swelling ratio) : the intensity rapidly decreases, and it reaches a minimum at very low R, at similar to 10% of the equilibrium swelling ratio, and then increases to a constant value. These phenomena reveal important aspects of the structure of the free volume in the APN and provide fundamental information about the swelling dynamics. The minimum of the o-Ps intensity is reached at around 1:1 water/monomer units molar ratio in the network. Surprisingly, a similar phenomenon was observed when the monomer itself was mixed with water. Molecular modeling by ab initio calculations indicates that a 1:1 ringlike cluster may be formed between water and DMAEMA. On the basis of these results it is concluded that the surface of the free volume units in the APN become covered with water molecules quickly by interacting with the PDMAEMA chains at the beginning of swelling. This indicates that the free volume in the PDMAEMA-l-PIB APN is not composed of independent pores but of interconnected channels which allow rapid diffusion of water molecules to cover the surface of the free volume units. This fast process results in a quick surface structure reorganization, i.e., enrichment of the surface of the channels by PDMAEMA segments leading to the corresponding rapid decrease of o-Ps formation intensity, and to the simultaneous collapse of PIE domains yielding increase of free volume in the network and positron lifetime at the beginning of swelling. Results of this study also allow us to predict that the combined method presented here, i.e., simultaneous swelling kinetics and positron annihilation investigations, can be widely applicable for gaining new information on free volume structure, swelling dynamics, and interactions between material components and swelling agents for a large variety of networks, gels, polyelectrolytes, amorphous materials, blends, composites, etc.