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Boron nitride (BN) is a member of Group III nitrides and continues to spark interest among the scientific community for its mechanical properties, chemical inertness, thermal conductivity, and electrical insulating properties. In this study, microwave plasma chemical vapor deposition is used to synthesize BN on silicon substrates. Feed gas mixtures of H2, NH3, and B2H6 are used for a range of systematically varied power, pressure, and flow rate conditions. Plasma optical emission from atomic boron is shown to increase nonlinearly by nearly a factor of five with decreasing chamber pressure in the range from 100 to 10 Torr. Copious amounts of atomic boron in the plasma may be beneficial under some growth conditions for producing high hardness boron-rich nitrides, such as B13N2, B50N2, or B6N, which, to date, have only been synthesized under high pressure/high temperature conditions. Despite the higher atomic boron emission in the plasma at low pressure, BN coatings grown at 15 Torr result in hexagonal BN (B/N ratio of 1), regardless of the B2H6 flow rate used in the range of 0.6–3.0 sccm.