A one-pot, two-step, four-component synthesis of benzo[c]pyrano[3,2-a]phenazine and bis-benzo[c]pyrano[3,2-a]phenazine derivatives was carried out by the reaction of 2-hydroxy-1,4-naphthoquinone, benzene-1,2-diamine, carbonyl compounds and alkylmalonates using new copper (II) ions complexes of guanine (2-amino-1H-purin-6(9H)-one) supported into MCM-41 (Cu-guanine-MCM-41) and SBA-15 (Cu-guanine-SBA-15) channels as efficient and heterogeneous catalysts in PEG. The desired products were obtained in good to excellent yields. The prepared catalysts have been extensively characterized by different methods and can be reused for several times without any significant loss of their catalytic activities. The phenazine derivatives were also tested for their antimicrobial activities.