Four-dimensional (4D) printing, combining three-dimensional (3D) printing with time-dependent stimuli-responsive shape transformation, eliminates the limitations of the conventional 3D printing technique for the fabrication of complex hollow constructs. However, existing 4D printing techniques have limitations in terms of the shapes that can be created using a single shape-changing object. In this paper, we report an advanced 4D fabrication approach for vascular junctions, particularly T-junctions, using the 4D printing technique based on coordinated sequential folding of two or more specially designed shape-changing elements. In our approach, the T-junction is split into two components, and each component is 4D printed using different synthesized shape memory polyurethanes and their nanohybrids, which have been synthesized with varying hard segment contents and by incorporating different weight percentages of photo-responsive copper sulfide-polyvinyl pyrrolidone nanoparticles. The formation of a T-junction is demonstrated by assigning different shape memory behaviors to each component of the T-junction. A cell culture study with human umbilical vein endothelial cells reveals that the cells proliferate over time, and almost 90% of cells remain viable on day 7. Finally, the formation of the T-junction in the presence of near-infrared light has been demonstrated after seeding the endothelial cells on the programmed flat surface of the two components and fluorescence microscopy at day 3 and 7 reveals that the cells adhered well and continue to proliferate over time. Hence, the proposed alternative approach has huge potential and can be used to fabricate vascular junctions in the future.