Ti(2)(Ti(0.16)Ni(0.43)Al(0.41))(3) is a novel compound (labeled as τ(6)) in the Ti-rich region of the Ti-Ni-Al system in a limited temperature range 870 < T < 980 °C. The structure of τ(6)-Ti(2)(Ti,Ni,Al)(3) was solved from a combined analysis of X-ray single crystal and neutron powder diffracton data (space group C2/m, a = 1.85383(7) nm, b = 0.49970(2) nm, c = 0.81511(3) nm, and β = 99.597(3)°). τ(6)-Ti(2)(Ti,Ni,Al)(3) as a variant of the V(2)(Co(0.57)Si(0.43))(3)-type is a combination of slabs of the MgZn(2)-Laves type and slabs of the Zr(4)Al(3)-type forming a tetrahedrally close-packed Frank-Kasper structure with pentagon-triangle main layers. Titanium atoms occupy the vanadium sites, but Ti/Ni/Al atoms randomly share the (Co/Si) sites of V(2)(Co(0.57)Si(0.43))(3). Although τ(6) shows a random replacement on 6 of the 11 atom sites, it has no significant homogeneity range (~1 at. %). The composition of τ(6) changes slightly with temperature. DSC/DTA runs (1 K/min) were not sufficient to define proper reaction temperatures due to slow reaction kinetics. Therefore, phase equilibria related to τ(6) were derived from X-ray powder diffraction in combination with EPMA on alloys, which were annealed at carefully set temperatures and quenched. τ(6) forms from a peritectoid reaction η-(Ti,Al)(2)Ni + τ(3) + α(2) ↔ τ(6) at 980 °C and decomposes in a eutectoid reaction τ(6) ↔ η + τ(4) + α(2) at 870 °C. Both reactions involve the η-(Ti,Al)(2)Ni phase, for which the atom distribution was derived from X-ray single crystal intensity data, revealing Ti/Al randomly sharing the 48f- and 16c-positions in space group Fd3̅m (Ti(2)Ni-type, a = 1.12543(3) nm). There was no residual electron density at the octahedral centers of the crystal structure ruling out impurity stabilization. Phase equilibria involving the τ(6) phase have been established for various temperatures (T = 865, 900, 925, 950, 975 °C, and subsolidus). The reaction isotherms concerning the τ(6) phase have been established and are summarized in a Schultz-Scheil diagram.