Polymorphs play an important role in mediating the physical and chemical properties of compounds. Three polymorphs were obtained from different solvents used in crystallization. A new polymorph of 5-methylsalicylic acid (γ-MSA) were obtained from acetic acid. The polymorphs α-MSA and β-MSA crystallized from water, and the mixed solvent containing methanol and water, respectively. The novel morphology of γ-MSA has been characterized by single–crystal X–ray diffraction, IR spectroscopy data, and powder X-ray diffraction. Single-crystal X-ray diffraction analysis shows that γ-MSA belongs to the monoclinic system with the P21/c space group. The parameters are listed as the following: a = 7.2795(5) Å, b = 15.2560(7) Å, c = 6.7170(4) Å, β=100.834(7)°, V = 762.83(8) Å3. In the novel polymorphic structure, classical hydrogen bonds of O–H···O can be obviously observed, through which a supramolecular architecture will be generated. Apart from the classical hydrogen bonds, the weak hydrogen bonds of C–H⋯O can be only found in form γ-MSA. The luminescent maximal are 394, 398 and 406 nm for α-MSA,β-MSA and γ-MSA, respectively. The order of the luminescent maximal peaks is listed as the following: α<β<γ. Single-crystal X-ray diffraction analysis results reveal that the order of the stacking interactions and the dihedral angles occurred between the carboxylic group and phenyl ring presents the following: α<β<γ. The Hirshfeld analysis further confirms that there exists the same sequence of the C···H intercontacts in α-, β- and γ-polymorphs. The contribution of the H···O/O···H close contacts in γ-MSA is the largest among these polymorphs, being confirmed by differential scanning calorimeter (DSC) data, which is in a good agreement with that of melting point. On the basis of analysis of DSC data and the fusion rules, the enthalpies (ΔH) and entropies (ΔS) can be estimated to be 29.5 kJ mol-1 and 69.4 J K-1 mol-1 for α; 31.1 kJ mol-1 and 72.8 J K-1 mol-1 for β, and 35.4 kJ mol-1 and 74.5 J K-1 mol-1 for γ), and these polymorphs are monotropically related. The sequences of melting point, enthalpies and entropies can be proposed: α<β<γ.