In this work, a new kind of butterfly-like molecules of oxacalix[2]arene[2]pyrazine (OAP) are reported, which exhibit typical characteristics of aggregation-induced emission (AIE) via the restriction of intramolecular vibration (RIV) mechanism. Unlike any of the reported RIV-type AIE molecules, the synthetic procedures of which are complicated and associated high costs, OAP AIEgens can be synthesized in a facile manner by a one-step catalyst-free reaction using commercially available materials. Notably, OAP AIEgens are ideal ligands for constructing metal-organic frameworks (MOFs) due to their built-in coordination sites of pyrazine groups. OAP-based MOFs exhibit multiple potential applications in reversible gas response, encrypted information storage, and construction of white light-emitting devices. This work enriches limited kinds of RIV-type AIEgens, offers additional selections of bridging ligands for constructing luminescent MOFs and provides a visualized prototype to understand the effect of RIV process on the luminescence property of MOFs.