Dumbbell-shaped amphiphiles based on an elongated rod segment can self-assemble into planar networks with in-plane hexagonally ordered pores in aqueous solution. On increasing temperature, the 2D networks change into hollow capsules passing through the closed sheets as an intermediate structure due to a LCST behavior of the oligoether dendritic exterior. The primary driving force for this interesting feature seems to originate from a consequence of the energy balance between hydrophobic interactions of anisotropic rod segments and alkyl chains, and repulsive interactions between dissimilar blocks. This dynamic structural variation triggered by external stimuli in a self-assembling system can provide a useful strategy to create smart supramolecular materials and biomimetic systems.