Nanostructured hollow multilayered tubes can be created by combining layer-by-layer (LbL) and template leaching. Such materials are of particular interest for tissue engineering since they allow the precise control of physical and biochemical cues of implantable devices. The tubes are based on polyelectrolyte multilayer films. The final tubular structures can be characterized by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), microscopy, swelling and mechanical tests, including dynamic mechanical analysis (DMA) in physiological simulated conditions. More robust films could be produced via chemical cross-linking with genipin. Water uptake decreases from about 390% to 110% after cross-linking. The cross-linked tubes are more suitable structures for cell adhesion and spreading. Potential applications include tissue engineering.