Energy shortage and environmental pollution have attracted long-term attention. In this study, CaO were prepared from waste eggshell (EGC), preserved egg shell (PEC), clam shell (CLC) and crab shell (CRC), which were then compared with commercial CaO (CMC) to catalyze microwave-assisted pyrolysis of waste cooking oil (WCO) for enrichment of aromatics in bio-oil. The characterization results indicated that EGC and CLC contained 95.54% and 95.61% CaO respectively, which were higher than that of CMC (95.11%), and the pore properties of EGC were the best. In addition, the effects of CaO type and catalytic mode on pyrolysis were studied. In CaO catalytic pyrolysis, CMC and CLC in-situ catalysis produced more aromatics than ex-situ catalysis, and PEC and CRC were more conducive to aromatics formation in ex-situ condition. EGC was conducive to produce benzene, toluene and xylene (BTX) both in in-situ (19.04%) and ex-situ (20.76%) catalytic pyrolysis. In CaO/HZSM-5 catalysis, the optimal dual catalytic mode for generating monocyclic aromatic hydrocarbons (MAHs) was Mode A (CaO separated from HZSM-5 for ex-situ catalysis), and EGC/HZSM-5 performed well in benzene, toluene and xylene (BTX) production.