In this work, two-dimensional surface quasi-crystal patterns were developed by using a novel azobenzene-containing amorphous material (IAC-4), which was newly synthesized for the application. IAC-4 contains a core of isosorbide moiety and two push-pull type azo chromophores as the inner part. The periphery of IAC-4 is functionalized with four cinnamate groups, which can undergo [2+2] photocycloaddition reaction upon UV light irradiation. The molecular design can allow IAC-4 to readily form surface relief structures upon Ar+ laser irradiation, and the formed structures can be further stabilized through a photo-cross-linking reaction induced by UV light irradiation. On the basis of the material, two-dimensional (2D) quasi-crystal structures with different rotation symmetries were successfully fabricated on the IAC-4 films by using the dual-beam multiple exposure technique. In contrast to the approach using photoresist, the quasi-crystal structures were fabricated through the photoinduced mass migration, and no subsequent wet-etch or dry-etch step was required in the process. The quasi-crystal structures with rotation symmetry as high as 60-fold could be feasibly fabricated through this approach. The surface patterns and fabrication method can be potentially applied in areas such as optics, communications, and security inspection.