A series of thermotropic liquid crystalline polyesters containing phosphorus and aromatic ether groups (TLCP-AEs) were synthesized from p-acetoxybenzoic acid (p-ABA), terephthalic acid (TPA), 4,4′-oxybis(benzoic acid) (OBBA), and acetylated 2-(6-oxid-6H-dibenz(c,e) (1,2) oxaphosphorin 6-yl) 1,4-benzenediol (DOPO-AHQ). The chemical structure and the properties of TLCP-AEs were characterized by Fourier-transform spectroscopy (FTIR), proton nuclear magnetic resonance spectroscopy (1H NMR), differential scanning calorimetry (DSC), X-ray diffraction (XRD), thermogravimetry analysis (TGA), scanning electronic microscopy (SEM), polarizing optical microscopy (POM), limiting oxygen index, and UL-94 tests, respectively. The results showed that TLCP-AEs had low and broad mesophase temperatures (230–400 °C). TLCP-AEs also showed excellent thermal stability; their 5%-weight-loss temperatures were above 440 °C and the char yields at 700 °C were higher than 45 wt %. All TLCP-AE polyesters exhibited high flame retardancy with a LOI value of higher than 70 and UL-94 V-0 rating. The SEM observation revealed that TLCP-AEs had good fibrillation ability. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1182–1189, 2010