This search used the low-cost boric acid and borax as a source of boron, urea as a nitrogen source, surface-active agent Dodecyl benzenesulfonic acid (SDBS) as a dispersant, and thus prepared different micro-morphology and crystallinity hexagonal boron nitride powders under a flowing ammonia atmosphere at a nitriding temperature of 900 °C. The effect of the surface-active agent (SDBS) content on the crystallinity and micro-morphology of hexagonal boron nitride powders was studied, and the corresponding relationship between micro-morphology and crystallinity was explored. The results showed that under a certain synthetic process (900 °C for 3 h), the surfactant content had affected the crystallinity and micro-morphology of h-BN powders. Without the added surfactant, the graphitization index (GI) was 3.61, and micro-morphology of h-BN powders. was spherical, the distribution of ball diameters was uneven, and there was also significant particle agglomeration, with some particles even exhibiting adhesion, sintering necks, and high sphericity and diameter. When the added SDBS percentages were 2%, 4% and 6%, the graphitization index (GI) decreased to 2.98, 2.58 and 2.41 respectively: the corresponding crystallinity improved significantly. When the surfactant SDBS content was higher (10%), the diameter distribution of the h-BN powders was even, but there was evidence of agglomeration of particles and particle adhesion. The crystallinity decreased when the GI value was increased to 4. When the surfactant SDBS content was 6%, the dispersion of h-BN powders was at its optimum, and the particle size distribution was at its most uniform. Meanwhile the GI value was at its lowest, and the crystallinity at its highest.