Polysubstituted naphthalenes and their analogues have been found in nature or synthesized, and have attracted increasing attention due to their numerous pharmacological and biological activities. The present study describes a synthesis of novel series of methoxynaphthalene derivatives using the Stobbe condensation reaction method. The chemical structures of these compounds were confirmed by spectroscopic techniques such as 1H and 13C NMR, IR, LC-HRMS spectral data and X-ray crystallography. The supramolecular assembly in the structures reported here is dominated by C—H···O hydrogen bonds for compounds 5, 6, 8, 11, 14 and 17 and O—H···O for compound 12. The molecules are also arranged by C–H···π interaction and/or π—π stacking, which are responsible for the formation and stability of the molecular assemblies. Hirshfeld surface analysis was also performed in order to obtain reliable structural information in concurrence with experimental results, and intermolecular interactions that exist inside the crystal have been investigated. Additionally, DFT calculations have been used to analyze the electronic and geometric frontier molecular orbital and Molecular Electrostatic Potential map analyses of the compounds were produced using the optimized structures.