A series of mercury(II) ionic liquids, [Cnmim][HgX3], where [Cnmim] = n-alkyl-3-methylimidazolium with n = 3, 4 and X = Cl, Br, have been synthesized following two different synthetic approaches, and structurally characterized by means of single-crystal X-ray structure analysis ([C3mim][HgCl3] (1), Cc (No. 9), Z = 4, a = 16.831(4) Å, b = 10.7496(15) Å, c = 7.4661(14) Å, β = 105.97(2)°, V = 1298.7(4) Å3 at 298 K; [C4mim][HgCl3] (2), Cc (No. 9), Z = 4, a = 17.3178(28) Å, b = 10.7410(15) Å, c = 7.4706(14) Å, β = 105.590(13)°, V = 1338.5(4) Å3 at 170 K; [C3mim][HgBr3] (3), P21/c (No. 14), Z = 4, a = 10.2041(10) Å, b = 10.7332(13) Å, c = 14.5796(16) Å, β = 122.47(2)°, V = 1347.2(3) Å3 at 170 K; [C4mim][HgBr3] (4), Cc (No. 9), Z = 4, a = 17.093(3) Å, b = 11.0498(14) Å, c = 7.8656(12) Å, β = 106.953(13)°, V = 1421.1(4) Å3 at 170 K). Compounds 1, 2, and 4 are isostructural and are characterized by strongly elongated trigonal [HgX5] bipyramids, which are connected via common edges in chains. In contrast, 3 contains [Hg2Br6] units formed by two edge-sharing tetrahedra. With melting points of 69.3 °C (1), 93.9 °C (2), 39.5 °C (3), and 58.3 °C (4), all compounds qualify as ionic liquids. 1, 2, and 4 solidify upon fast cooling as glasses, whereas 3 crystallizes. Cyclic voltammetry shows two separate, quasi-reversible redox processes, which can be associated with the 2Hg2+/Hg22+ and Hg22+/2Hg redox couples.