In the Raman spectrum of B-type carbonated apatites, the ν1 CO32- mode (at ∼1070 cm-1) overlaps the ν3 PO43- band. The latter is readily observed where the CO32- content is low (up to ∼3 wt%). The CO32- content of bone is considerably higher (∼7-9 wt%). As a result, the ν3 PO43- band becomes completely obscured. The 1000-1100 cm-1 spectral range of carbonated apatite is frequently considered a combined ν3 PO43- and ν1 CO32- region. Here, high-resolution polarized Raman spectroscopy (step size of 0.74 ± 0.04 cm-1) provides new insights into synthetic hydroxyapatite (HAp) obtained as micrometer-sized fibers. Compared to bone mineral (deproteinized bovine bone), spectral features of HAp fibers are highly resolved. In particular, the ν3 PO43- band resolves into nine distinct sub-components: 1028, 1032, 1040, 1043, 1047, 1053, 1055, 1062, and 1076 cm-1. Parameters including full width half-maximum, intensity, area fraction, intensity ratio, and area fraction ratio vary between parallel and perpendicular polarized configurations. It is likely that the ν1 CO32- band of B-type carbonated apatites may contain a small but not insignificant contribution from the 1076 cm-1 sub-component of the ν3 PO43- band. Furthermore, the 1076 cm-1/1047 cm-1 ratio changes between parallel and perpendicular scattering configurations, suggesting that the contribution of the 1076 cm-1 sub-component may vary as a function of local orientation of bone mineral, thus skewing the ν1 CO32- band and compromising accurate estimation of carbonate-to-phosphate ratios in B-type CO32- substituted apatite.