Fluorinated molecules have been used extensively in pharmaceutical, chemical and polymer industries. Indeed, the presence of fluorine provides unique but important physicochemical properties to the fluorinated molecules. In this review, we have discussed the effects of fluorine on the hydrogen bond network, photophysical and solvation behavior of the fluorinated molecules which have been obtained by the state of art spectroscopic and molecular dynamics simulation techniques. The substitution of fluorine in alcohols reorganizes the hydrogen bond network in its aqueous mixture by changing the orientation of water from its hydrophilic to the hydrophobic terminal. The fluorous (F...F) interaction has been found to affect photophysical and solvation properties of the fluorinated molecules significantly. The solvation time scale of the fluorinated molecules gets slower due to the fluorous interaction between probe and solvent molecules. The understanding of the role of fluorine on the hydrogen bond network, photophysical and solvation properties can be useful for the stepwise justification of the unique physicochemical properties of fluorinated molecules.