As the lifeline of almost all living tissues, blood vessels are a major focus of tissue-regenerative therapies. Rebuilding blood vessels has vast implications for the study of vascular growth and treatment of diseases in which vascular function is compromised. Toward this end, human pluripotent stem cells have been widely studied for their differentiation capacity toward vascular lineages. We demonstrate methods to derive a bicellular population of early specialized vascular cells from human pluripotent stem cells, to differentiate these toward mature endothelial cells and pericytes, and to utilize a collagen scaffold to facilitate organization into vascular networks.