Hexagonal boron nitride was synthesized from boron oxide and sodium amide in ammonia gas stream. The reaction mechanisms and characteristics of as synthesized boron nitride was investigated by means of TG, DTA, IR, XRD, SEM and PSA. The results are ; 1) hexagonal boron nitride was synthesized from reactions at temperatures above 40$0^{circ}C$ 2) Sodium metaborate was present as by-product after reaction so that the reaction mechanism is reduced as follows : 2B2O3＋3NaNH2longrightarrowBN＋3NaBO2＋2NH3. 3) boron nitride obtained at the reaction temperature below 40$0^{circ}C$ is found to have random layer strudcture but the structure transits to ordered layer structure rapidly with increasing reaction temperature, showing separation of (101) differaction line from (10)band in XRD pattern of the reaction product at 50$0^{circ}C$.