In this record we provide data to support our recent findings for the fabrication of Unsaturated Carbon Nanostructures with Regularly Fused Pentagon–Heptagon Pairs. Multiple fused pentagon–heptagon pairs are frequently found as defects at the grain boundaries of the hexagonal graphene lattice and are suggested to have a fundamental influence on graphene-related materials. However, the construction of sp2-carbon skeletons with multiple regularly fused pentagon–heptagon pairs is challenging. In this work, we found that the pentagon–heptagon skeleton of azulene was rearranged during the thermal reaction of an azulene-incorporated organometallic polymer on Au(111). The resulting sp2-carbon frameworks were characterized by high-resolution scanning probe microscopy techniques and feature novel polycyclic architectures composed of multiple regularly fused pentagon–heptagon pairs. Moreover, the calculated analysis of its aromaticity revealed a peculiar polar electronic structure.