Abstract 13C NMR spectra at room temperature and the temperature dependences of 1H T1 in the solid state were measured in [Ni1−xPdxX(chxn)2]X2 (X: Cl, Br; chxn: 1R,2R-cyclohexanediamine; 0.0 ≤ x ≤ 1.0), where antiferromagnetically coupled paramagnetic –X–Ni3+–X–Ni3+–X– chains were formed at x = 0.00, while the mixed-valence –X–Pd2+–X–Pd4+–X– state was made at x = 1.00. 13C signals at α-carbons in chxn coordinating to Pd atoms showed a doublet assignable to Pd2+ and Pd4+ in x = 1.00, while, with a slight decrease of x from 1.00, a clear broadening and a shift to low-field of signals, indicating conversion into the averaged Pd3+ state, were observed. This can be explained by the fluctuation of the Pd valency caused by neighboring paramagnetic Ni3+ sites introduced in small amounts in the 1-D chain. The x dependences of the chemical shifts of β- and γ-carbons are also attributable to the effect from a partial mixing of the paramagnetic Pd3+ sites. The values of 1H T1 and its temperature dependence observed in the ranges of 100–300 K and x ≤ 0.13 for [Ni1−xPdxBr(chxn)2]Br2 could be explained by a model of strong exchange interactions between Ni3+ and Pd3+ as well as Ni3+ sites. Gradual changes in the T1 value and slope with increasing x from 0.00 to 0.93 are attributable to the variation of the exchange interaction value, which depends upon the number of Ni–Ni pairs.