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In this study, we address the selection rules with respect to thepolarization of the optical excitation of two colour centres in 4H-SiC and6H-SiC with potential for applications in quantum technology, the divacancy andthe nitrogen-vacancy pair. We show that the photoluminescence (PL) of the axialconfigurations of higher symmetry (C3v) than the basal ones (C1h) can becancelled using any excitation (resonant or non-resonant) with polarizationparallel to the crystal axis (EL||c). The polarization selection rules aredetermined using group-theoretical analysis and simple physical argumentsshowing that phonon-assisted absorption with EL||c is prohibited despite beingformally allowed by group theory. A comparison with the selection rules for thesilicon vacancy, another defect with C3v symmetry, is also carried out. Usingthe selection rules, we demonstrate selective excitation of only one basaldivacancy configuration in 4H-SiC, the P3 line and discuss the higher contrastand increased Debye-Waller factor in the selectively excited spectrum.

Selection rules in the excitation of the divacancy and the nitrogen-vacancy pair in 4H- and 6H-SiC