Poly(vinylidene fluoride) (PVF2) of a linear polymer molecular chain is useful to bridge 1–2 dimensional (D) networks by H-bonding in a dilute medium such as N,N-dimethylformamide (DMF). As a result, a model 1– 2D PVF2 molecule tunes selective DMF configurations. This is studied with C=O (DMF) group vibration bands which vary in how DMF molecules H-bond through PVF2 as per its dosage and local structure. The PVF2 content is varied in small steps over 0.1 to 100 g/L in DMF solutions in attenuating model structures in terms of the IR bands. Virgin DMF has three C=O stretching bands ν1 C=O, ν2 C=O, and ν3 C=O of 1652, 1670, and 1724 cm−1 of three different configurations. A head-on-H-bonding between C=O groups of two DMF molecules strongly H-bonds them in a bismolecular assembly that shares the maximum intensity in the lowest frequency 1652 cm−1 band. More molecules add-up giving rise to a promoted value of 1670 cm−1, while the third band of 1724 cm−1 (poor intensity) briefs only a weak side-by-side H-bonding in a different configuration. These bands change selectively upon adding PVF2 in a polymer solution. The ν2 C=O peak intensity arises in a sharp peak at 6.5 g/L PVF2 at the expense of the ν1 C=O band, while the integrated intensity varies through two peaks at 1.3 and 20.1 g/L PVF2 in a percolative effect on the C=O vibrations that converge in association with PVF2 in preferential configurations. Model configurations are proposed based on the various ways the PVF2 probes the ν1–3 C=O IR bands.