AbstractSelf‐assembled reactions of 2,6‐dipicolinoylbis(N,N‐diethylthiourea) (H2L) with Mn(CH3COO)2 ⋅ 4H2O and LnCl3, where Ln = La, Nd, Sm, Gd, Dy, Er in MeOH lead to formation of stable trinuclear complexes of the composition [LnMn2(L)2(μ1,3‐CH3COO)2X] (MnIILnIIIMnII), where X− can be κ2‐CH3COO− or κ1‐CH3COO−. Single crystal X‐ray studies reveal their symmetric structures comprising one central Ln(III) ion, two terminal Mn(II) ions sandwiched by two doubly deprotonated ligands {L2−}. The magnetic properties of MnIILaIIIMnII and MnIIGdIIIMnII complexes are successfully simulated using symmetrical magnetic interaction models, giving the best fitted parameters: JMn‐Mn=−0.120(1) cm−1, gMn=1.99(1), TIP=4.45(7) ⋅ 10−4 cm3 mol−1 K for MnIILaIIIMnII and JGd‐Mn=0.042(1) cm−1, JMn‐Mn=−0.076(1) cm−1, gMn=1.96(1), gGd=2.01(1) and TIP=3.59(14) ⋅ 10−4 cm3 mol−1 K for MnIIGdIIIMnII complex. The magnetic interactions between the Mn(II) and Ln(III) ions in the other MnIILnIIIMnII complexes are studied by comparing their χM values to the sum of χM values of the MnIILaIIIMnII and the analogous ZnIILnIIIZnII complexes. The MnIIErIIIMnII complex reveals a strong ferromagnetic interaction, while the Sm, Nd, Gd and Dy complexes show weak ferromagnetic interactions.