The combination of two-dimensional (2D) materials into vertical heterostructures has emerged as a promising path to designer quantum materials with exotic properties. Here, we extend this concept from inorganic 2D materials to 2D metal-organic frameworks (MOFs) that offer additional flexibility in realizing designer heterostructures. We successfully fabricate a monolayer 2D Cu-dicyanoanthracene MOF on a 2D van der Waals NbSe2 superconducting substrate. The structural and electronic properties of two different phases of the 2D MOF are characterized by low-temperature scanning tunneling microscopy (STM) and spectroscopy (STS), complemented by density-functional theory (DFT) calculations. These experiments allow us to follow the formation of the kagome band structure from Star of David-shaped building blocks. This work extends the synthesis and electronic tunability of 2D MOFs beyond the electronically less relevant metal and semiconducting surfaces to superconducting substrates, which are needed for the development of emerging quantum materials such as topological superconductors.