Aromatic polybenzoxazoles (PBOs) are very promising materials for civil, aerospace and electronics industries due to their outstanding mechanical properties, good thermooxidative stability and chemical resistance. However, the feasibility of the wide applications is hindered due to the difficulty of their processing derived from the very rigid structure. Poly(aryl-ether benzoxazole) random copolymers (PAEXBOx) were prepared by nucleophilic polycondensation. Ary-ether ketone and aryl-ether sulfone segments along with flexible linkages and bulky groups were introduced to provide PAEXBOx with good solubility in organic solvents. PAEXBOx exhibit the improved Tgs, and intermediate properties between pristine PBOs and poly(acryl ether)s (PAEs). The structure and properties of the polymers were systematically characterized.