We developed the first nanopore reference materials in the world using synthetic fused silica and polycarbonate for positron hole-size measurements, which are intended for use in controlling the precision as well as in validating the condition of conventional bulk positron lifetime measurements. The first one (fused silica), having a certified value of 1.63 ns for the third lifetime component, had been released in July 2007 as the certified reference material (CRM) of AIST, followed by the second CRM (polycarbonate) with a certified value of 2.10 ns, released in May 2009. The established CRMs are promising in supporting R&Ds of innovative functional materials with engineered nanoporosity, such as inter-layer dielectrics for next generation semiconductors and high-performance separation membranes.