In the present work, we characterize the amphibole Na(NaMg)Mg5Si8O22(OH)2 synthesized at 0.4 GPa and 750, 800, and 850 °C, and 0.5 GPa, 900 °C. Experiments at 800 and 900 °C yielded crystals suitable for single-crystal data collection. Structure refinement shows that synthetic Na(NaMg)Mg5Si8O22(OH)2 has P21/m symmetry at room T. The two non-equivalent tetrahedral double-chains differ in their degree of stretching and kinking. The infrared spectrum of synthetic Na(NaMg)Mg5Si8O22(OH)2 has two well-defined absorption bands at 3742 and 3715 cm−1 which can be assigned to O-H bands associated with the two independent anion sites (O3A and O3B) in the structure. The higher frequency band is assigned to the shorter O3B-H2 bond, and the lower frequency band is assigned to the longer O3A-H1 bond. The broader shape of the 3743 cm−1 band is consistent with a stronger interaction of the H2 atom with ANa, which is confirmed by structure refinement. Increasing T of synthesis causes a progressive departure from the ideal stoichiometry via the A□1BMg1ANa−1BNa−1 substitution, as confirmed by EMPA, structure refinement, and FTIR spectroscopy.