In this work, complexes of β-cyclodextrin and the two solid forms of furosemide were prepared and characterized for their potential pharmaceutical applications, with the interactions between the two compounds being studied in the solution and solid states. The solubility studies revealed different behaviors of the polymorphs. In particular, it was observed that the binary complex significantly increased the solubility of furosemide form I in the gastric simulated fluid, which resulted in a rise in the bioavailability of this formulation after oral administration. In addition, results using ssNMR, FT-IR, DSC, TGA, SEM and XRPD provided evidence of the formation of complexes after utilizing kneading and freeze-drying methods. A comparison with previous developed complexes that used maltodextrin as the ligand was performed. Our results suggest that these novel supramolecular complexes showed promise to be used in drug delivery systems with an application in pharmaceutical formulations.