In the present work, we investigated donor-acceptor-pair emission in N-B doped fluorescent 6H-SiC, by means of photoluminescence, Raman spectroscopy, and angle-resolved photoluminescence. The photoluminescence results were interpreted by using a band diagram with Fermi-Dirac statistics. It is shown that with N and B concentrations in a range of 1018 cm−3 the samples exhibit the most intense luminescence when the concentration difference (n-type) is about 4.6x1018 cm−3. Raman spectroscopy studies further verified the doping type and concentrations for the samples. Furthermore, strong luminescence intensity in a large emission angle range was achieved from angle-resolved photoluminescence. The results indicate N-B doped fluorescent SiC as a good wavelength converter in white LEDs applications.