Finding new ways to construct crystalline multiple-component covalent organic frameworks (COFs) has become an important focus. Herein we report the synthesis of three novel COFs containing a homogeneous and heterogeneous distribution of pi-conjugated dehydrobenzoannulene (DBA) vertex units. The COFs were synthesized by reacting different tatios of C-3-syrninetric DBA catechol, monomers with C-2-symmetric pyrene-2,7dibotonic acid (PDBA) to yield three COFs, Py-DBACOF 1, Py-DBA-COF 2, and Py-MV-DBA-COF. All three materials are highly crystalline and display unique luminescent properties in the solid state.