The structure of folic acid dihydrate has been investigated in the solid state by means of a synergistic approach combining Raman spectroscopy, X-ray powder diffraction, and cutting-edge calculation methods. The comparison of the computed and measured Raman spectra was used to support the finding of a new crystalline form. Crystalline folic acid·2H2O has also been used in the preparation, via solvent free methods, of amorphous multicomponent materials and salts by reacting folic acid with LiOH, NaOH, Na2CO3, and Ca(OH)2, which were also investigated by X-ray powder diffraction, thermogravimetric analysis, differential scanning calorimetry, and intrinsic dissolution rate, and this has been compared with the values of the native vitamin. The preparation and characterization of the amorphous, hydrated adduct with LiCl is also reported.