The reaction of 4‐amino‐5‐methyl‐2H‐1,2,4‐triazole‐3(4H)‐thione (AMTT, 1) with 4‐methoxy benzaldehyde and 3‐methoxybenzaldehyde in methanol led to the iminic derivatives 4‐(4‐methoxybenzylideneamino)‐5‐methyl‐2H‐1,2,4‐triazole‐3(4H)thione (2, L1) and 4‐(3‐methoxybenzylideneamino)‐5‐methyl‐2H‐1,2,4‐triazole‐3(4H)‐thione (3, L2). The reaction of the latter with [(PPh3)2CuCl] in methanol solution gave the first CuI complex of 3, [(PPh3)2CuCl(L2)] (4) and in chloroform solution the complex [(PPh3)2CuCl(L2)]·2CHCl3 (5). All compounds were characterized by infrared spectroscopy, elemental analyses as well as by X‐ray diffraction studies. Crystal data for 2 at −80 °C: space group P21/c with a = 1351.3(3), b = 399.4(1), c = 2225.2(5) pm, β = 96.50(2)°, Z = 4, R1 = 0.0667, for 3 at −80 °C: space group R3c with a = b = 3020.4(2), c = 708.2(1) pm, Z = 18, R1 = 0.0435, for 4 at −80 °C: space group P21/c with a = 1427.8(1), b = 1129.0(1), c = 2622.8(2) pm, β = 97.19(1)°, Z = 4, R1 = 0.0517 and for 5 at −80 °C: space group ${\rm P}{\bar 1}$ with a = 1280.5(1), b = 1316.1(1), c = 1731.4(1) pm, α = 78.14(1)°, β = 86.06(1)°, γ = 64.69(1)°, Z = 2, R1 = 0.0525.