Nuclear magnetic resonance (NMR) and broadband dielectric spectroscopies (BDS) were used to analyze the molecular dynamics in P10.3H Podand. The temperature studies of NMR line and magnetic spin–lattice relaxation times accompanied by DS investigation enabled us to distinguish three main dynamical processes connected with the motions of the P10.3H Podand chains. In the low‐temperature region the magnetic relaxation was associated with fast axial C3 rotation of methyl groups. Moreover, two other independent processes were observed and interpreted as (i) segmental motion of both oxyethylene and ethylene units, and (ii) the overall motion involved in the melting process.magnified image