New 1,8-naphthalimides with thiophene or bithiophene structure attached by an imine linkage to naphthalene core were synthesized. The structures of obtained compounds were characterized by FTIR, 1H NMR spectroscopy, elemental analysis and for elected compounds by HRMS (ESI) spectrometry. Thermal, optical and electrochemical properties of obtained 1,8-naphthalimides were investigated. Most of them exhibited glass-forming properties with glass transition temperatures in the range of 73–278 °C. Optical properties of the prepared compounds were examined by UV–vis and photoluminescence (PL) measurements. They emitted light in chloroform solution with emission maximum at ca. 500 nm with the highest quantum yield of fluorescence around 0.46 and green one in NMP solution. In blend with PMMA blue emission was observed with the highest quantum yield of fluorescence around 0.24. All compounds are electrochemically active, and undergo reversible reduction and irreversible or quasi-reversible oxidation process as was found in cyclic and differential pulse voltammetry (CV and DPV) studies. They showed electrochemical band gaps in the range 2.28–2.68 eV. Additionally, the electronic properties, that is, orbital energies and resulting energy gap were calculated by density functional theory (DFT). Additionally, selected compounds were preliminary tested as electroluminescence materials in devices with structure ITO/PVK:NI blend/Al.