A new functionalized triethoxysilane bearing an X-shaped, anthracene-based semiconducting molecule on one arm was designed and synthesized as a precursor for the preparation of a self-assembled monolayer (SAM) on a SiO2 substrate. 3-Isocyanatopropyl triethoxysilane was reacted with a monohydroxyl-terminated X-shaped, anthracene-based semiconducting molecule in the presence of tin catalyst. The 6-(5( (6- ( (5-hexylthiophen-2-yOethyny1)-9,10-bis (ph enylethyny1)anthracen-2-yOethynypthiophen-2-yOhexyl 3-(triethoxysily1)propylcarbamate (BATHT-TEOS) was found to be stable and sufficiently reactive to form organic monolayers on hydroxylated SiO2 surfaces. The structures and properties of these SAMs were investigated using X-ray photoelectron spectroscopy, UV vis absorption spectroscopy, photoluminescence (PL) spectroscopy, laser scanning confocal microscopy PL spectrometry, and spectroscopic ellipsometry. In this work, BATHT-SAM was employed as an interfacial layer on SiO2 to fabricate ultrathin film transistors (UTFTs, active layer thickness 16.09 nm). The device UTFT-I, made of 0.06 wt % S,S'-(9,10-bis(phenylethynyl)anthracene-2,6-diy1)bis(ethyne-2,1-diyObis(2hexylthiophene) (BATHT) solution on an n-octyltrichlorosilane-SAM/Si02 layer, showed no gate effect for the carrier transport behavior; however, the device UTFT-II, fabricated on BATHT-SAM/Si02, exhibited field effect mobilities of 0.04 cm2 Nr1 s (10,off 6.3 x 103 to 1.0 x 104). This can be attributed to the effect of BATHT-SAM inducing uniform coverage and ordering of BATHT molecules as an upper layer.