Six new uranium thiophosphates, Cs5Na6[U(PS4)(4)](PS4) (1), Rb5Na3[U(PS4)(4)] (2), CsNa[U(PS4)(2)] (3), Cs1.67Na0.52I0.19[U(PS4)(2)] (4), Cs1.033Na1.343I0.376[U(PS4)(2)] (5), and Rb1.35Na0.93I0.28[U(PS4)(2)] (6), were obtained from halide flux reactions and characterized using single-crystal X-ray diffraction. The structures of these compounds consist of a pseudotetrahedral uranium unit that in combination with a set of PS4 group coordination modes can result in an isolated [U(PS4)(4)](8-) unit, a [U(PS4)(2)](2-) chain, or a [U(PS4)(2)](2-) slab. Optical and magnetic properties of 3 and 4 were collected. Both compounds exhibit paramagnetic behavior, and CsNa-[U(PS4)(2)] (3) exhibits a magnetic transition at 200-225 K between two paramagnetic states that both have similar effective magnetic moments of 4.13 and 4.19 mu(B)/formula unit, and strong antiferromagnetic interactions with theta = -183 and -172 K, for the high- and low-temperature states, respectively.