New multi-branched molecules have been synthesized through Horner-Emmons reactions using 10-((triisopropylsilyl)ethynyl) anthracene-9-carbaldehyde as dendrons and octaethyl benzene-1,2,4,5-tetrayltetrakis(methylene) tetraphosphonate as a reactive core unit; these molecules have been fully characterized. Two anthracene-based star-shaped molecules exhibit good solubility in common organic solvents and good self-film forming properties. The four-armed molecule, 4(TIPS-ant)-benzene is intrinsically crystalline as they exhibit well-defined X-ray diffraction patterns from relatively uniform orientations of molecules. According to the AFM analysis, 4(TIPS-ant)-benzene helps in attaining good network interconnection of the carrier transport channel, which is responsible for the charge carrier mobility in solution-processed organic semiconductors for organic thin film transistor (OTFT).