Polyalkylenebenzoxazoles of high molecular weight (inherent viscosity values from 0.76 to 2.95) were prepared from 4,6-diaminoresorcinol dihydrochloride and aliphatic diacids in polyphosphoric acid by heating at 180 to 200-degrees-C for 3-5 h. Melting points of the polymers ranged from 148 to 423-degrees-C, depending on the length of the alkylene chain. Glass transition temperatures were relatively low, ranging from 50 to 100-degrees-C and did not show the pronounced odd/even effect noted for melting points. In all cases, rapid weight loss occurred above 400-degrees-C. No evidence for the formation of a molecular composite was observed in an attempt to prepare in situ a rod-like polybenzoxazole in a polyalkylenebenzoxazole.