We report on the first polarimetric study of (3200) Phaethon, the target of JAXA’s DESTINY+ mission, in the negative branch to ensure its anhydrous nature and to derive an accurate geometric albedo. We conducted observations at low phase angles (Sun-target-observer angle, α = 8.8–32.4°) from 2021 October to 2022 January and found that Phaethon has a minimum polarization degree Pmin = −1.3 ± 0.1  per cent, a polarimetric slope h = 0.22 ± 0.02  per cent deg−1, and an inversion angle α0 = 19.9 ± 0.3°. The derived geometric albedo is pV = 0.11 (in the range of 0.08–0.13). These polarimetric properties are consistent with anhydrous chondrites, contradict hydrous chondrites, and typical cometary nuclei.