X-ray powder diffraction, differential scanning calorimetry (DSC)/thermogravimetry (TG) and single-crystal neutron diffraction methods were used to investigate triammonium hydrogen disulfate (NH4)3H(SO4)2 (TAHS) in the temperature range between 293 and 493 K. The temperature-dependent X-ray powder diffraction measurements show a clear hysteresis of the I \leftrightarrow II phase transition of TAHS with transition temperatures of T
up = 412.9 (1) K on heating and of T
down = 402.6 (1) K on cooling. From the existence of hysteresis and from the jump-like changes of the lattice parameters, the I \leftrightarrow II phase transition of TAHS is considered to be first order. With DSC/TG measurements we confirmed that there is only one phase transition between 293 and 493 K. Through careful investigation on single crystals of TAHS using neutron diffraction, the correct space group (C2/c) of room-temperature TAHS-II phase was confirmed. Crystal structure analysis by single-crystal neutron diffraction showed a strongly elongated displacement ellipsoid of the proton which lies in the middle of the (SO4)H(SO4) dimer with \bar 1 local symmetry. The protons of the NH4 groups also show strongly enlarged anisotropic mean-square displacements. These findings are interpreted in terms of a characteristic proton disorder in the TAHS-II phase.