Six azaphilonoid derivatives, including two new blue fluorescent monapurfluores A (1) and B (2), two known pyridine-containing molecules, monascopyridines C (3) and D (4), and two known monasfluores A (5) and B (6), were isolated and characterized from red mold rice fermented by Monascus purpureus NTU 568. Structural elucidation of new isolates was based on nuclear magnetic resonance (1H- NMR, 13C-NMR, COSY, HMQC, and HMBC) and other spectroscopic analyses. Bioactivity evaluation indicated that 1-6 possessed anti-inflammatory activities with dose-dependent relationships for lipopolysaccharide (LPS)-induced nitric oxide production. Furthermore, 1-4 also showed moderate antiproliferative effects against human laryngeal carcinoma (HEp-2) (IC(50) = 14.81~20.06 μg/mL) and human colon adenocarcinoma (WiDr) (IC(50) = 12.89~21.14 μg/mL).