The effect of solvents (H-donor; H-acceptor and both H-acceptor and H-donor solvents) casted on the poly(ethylene glycol) (PEG) samples with varying molecular weights (2000, 4600, 8000 and 10000) was performed solid-state characterization by Fourier Transform Infrared Spectroscopy (FTIR), Raman and X-ray Diffraction (XRD) in submitted study. In this study, spectral differences were classified with respect to stretching, bending, rocking, angle bending, internal rotation frequencies and low-frequency Raman region according to functional groups and thus crystallinity were evaluated as related with solvent character and polymer molecular weight. Crystalline and amorphous regions in the XRD diffractograms have been found by Polynomial Regression method through Microsoft Office Excel program and subsequently, crystallinity percentages were evaluated. From XRD spectra of PEG/solvent systems, the highest decrease in crystallinity percent has been detected in the sample cast from tetrahydrofuran. On the other hand, the largest frequency shifts of various stretching and bending vibrations of PEG have been observed for the samples cast from chloroform and especially tetrahydrofuran in FTIR and Raman spectra.