Pursuing long-term self-healing infrastructures has gained popularity in the construction field. Vascular networks have the potential to achieve long-term self-healing in cementitious infrastructures. To avoid further monitoring of non-cementitious tubes, sacrificial material can be used as a way of creating hollow channels. In this research, we report a new method for fabrication of complex 3D internal hollow tunnels using 3D printing of polyvinyl alcohol (PVA). The behaviour of 3D printed PVA structures in cement pastes was investigated using computed-tomography (CT) combined with X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), and scanning electron microscopy with energy dispersive spectroscopy (SEM/EDX). Results showed that (i) 1300 min were needed to fully dissolve 1 g of a 3D printed PVA structure, and different pH solutions did not significantly change the PVA dissolving process compared with a neutral environment; (ii) a low water/cement ratio can minimize early stage cracking resulting from PVA expansion; (iii) and PVA-cement interaction products were mainly calcite and a Ca-polymer compound. In conclusion, controlling the PVA expansion by decreasing the water/cement (w/c) ratio provides a promising approach to achieve 3D hollow channels in cement and, therefore, makes it possible to create complex tunnels within self-healing cementitious materials.