The reactions of Ti with in situ formed polythiophosphate fluxes of A₂S₃ (A = Rb, Cs), P₂S₅, and S at 500 °C result in the formation of two new quaternary titanium thiophosphates with compositions Rb₃Ti₃(P₄S₁₃)(PS₄)₃ (1) and Cs₂Ti₂(P₂S₈)(PS₄)₂ (2). Rb₃Ti₃(P₄S₁₃)(PS₄)₃ (1) crystallizes in the chiral hexagonal space group P6₃ (No. 173) with lattice parameters a = 18.2475(9) Å, c = 6.8687(3) Å, V = 1980.7(2) ų, Z = 2. Cs₂Ti₂(P₂S₈)(PS₄)₂ (2) crystallizes in the noncentrosymmetric monoclinic space group Cc (No. 9) with a = 21.9709(14) Å, b = 6.9093(3) Å, c = 17.1489(10) Å, β = 98.79(1)°, V = 2572.7(2) ų, Z = 4. In the structure of 1 TiS₆ octahedra, three [PS₄] tetrahedra, and the hitherto unknown [P₄S₁₃]^6- anion are joined to form two different types of helical chains. These chains are connected yielding two different helical tunnels being directed along [001]. The tunnels are occupied by the Rb⁺ ions. The [P₄S₁₃]^6- anion is generated by three [PS₄] tetrahedra sharing corners with one [PS₄] group in the center of the starlike anion. The P atoms of the three [PS₄] tetrahedra attached to the central [PS₄] group define an equilateral triangle. The [P₄S₁₃]^6- anion may be regarded as a new member of the [P_nS_3n+1]^(n+2)- series. The structure of Cs₂Ti₂(P₂S₈)(PS₄)₂ (2) consists of the one-dimensional polar tunnels containing the Cs⁺ cations. The rare [P₂S₈]^4- anion which is composed of two [PS₄] tetrahedra joined by a S₂^2- anion is a fundamental building unit in the structure of 2. One-dimensional undulated chains being directed along [100] are joined by [PS₄] tetrahedra to form the three-dimensional network with polar tunnels running along [010]. The compounds are characterized with IR, Raman spectroscopy, and UV/vis diffuse reflectance spectroscopy.