FTIR signature of neat tetrahydrofuran (THF), methanol (MeOH) and their binary solutions at various molefractions (0.8:0.2 (THF:MeOH), 0.6:0.4, 0.4:0.6 and 0.2:0.8) have been recorded. Density Functional Theory (DFT) calculations have also been carried out on THF, MeOH multimers and possible THF-MeOH complex molecules. The results of FTIR studies and DFT calculations confirm the formation of 1:3 (THF:MeOH) and 1:4 complex structures with (MeOH)O - H⋯O(THF), (MeOH methyl)C - H⋯O(THF) and (THF methylene)C - H⋯O(MeOH) H-bond interactions. (MeOH)O - H⋯O(MeOH) homointeractions among the MeOH trimers and tetramers are stronger than the THF-MeOH heterointeractions in complexes. But, the stability of 1:4 complexes is more than that of the trimers and tetramers as inferred from the interaction energy values obtained by DFT calculations. Time Domain Reflectometry (TDR) study has also been carried out on the THF-MeOH binary solutions in the frequency range 10 MHz-30 GHz at 298 K. The results of dielectric studies have been correlated with that of FTIR studies and DFT calculations.