A series of novel 6-aminophenazine-1-, 7-aminophenazine-1- and 8-aminophenazine-1-carboxylate derivatives were synthesized by a facile method, and their structures were characterized by (1)H NMR, (13)C NMR and high-resolution mass spectrometry. Some unexpected byproducts V-7b-V-8d were noticed and isolated, and their structures were identified by 2D NMR spectra including heteronuclear multiple-quantum coherence (HMQC), heteronuclear multiple-bond correlation (Hmbc) and H-H correlation spectrometry (H-H COSY) approach. Their fungicidal activities against five fungi were evaluated, which indicated that most of the title compounds showed low fungicidal activities in vitro against Alternaria solani, Cercospora arachidicola, Fusarium omysporum, Gibberella zeae, and Physalospora piricola at a dosage of 50 microg mL(-1), while compounds IV-6a and IV-6b exhibited excellent activities against P. piricola at that dosage. Compound IV-6a could be considered as a leading structure for further design of fungicides.