In this study, we fabricated a poly(dimethylsiloxane) (PDMS) surface coated with polydopamine (PDA) to enhance cell adhesion. PDA is well known for improving surface adhesion on various surfaces due to the abundant reactions enabled by the phenyl, amine, and catechol groups contained within it. To confirm the successful surface coating with PDA, the water contact angle and X-ray photoelectron spectroscopy were analyzed. Human umbilical vein endothelial cells (HUVECs) and human-bone-marrow-derived mesenchymal stem cells (MSCs) were cultured on the PDA-coated PDMS surface to evaluate potential improvements in cell adhesion and proliferation. HUVECs were also cultured inside a cylindrical PDMS microchannel, which was constructed to mimic a human blood vessel, and their growth and performance were compared to those of cells grown inside a rectangular microchannel. This study provides a helpful perspective for building a platform that mimics in vivo environments in a more realistic manner.