A quasiperiodic Pb monolayer has been formed on the five-fold surface of the Al-Pd-Mn quasicrystal. Growth of the monolayer proceeds via self-assembly of an interconnected network of pentagonal Pb stars, which are shown to be tau-inflated compared to similar structural elements of the quasiperiodic substrate. Measurements of the electronic structure of the system using scanning tunnelling spectroscopy and ultra-violet photoemission spectroscopy reveal that the Pb monolayer displays a pseudo-gap at the Fermi level which is directly related to its quasiperiodic structure.