We report the formation and subsequent topochemical polymerization of semi-fluorinated self-assembled monolayers (SAMs) containing diacetylene groups. The SAMs used were formed via the adsorption of the following derivatives: CF3(CF2)(n()CH2)(16)C dropC-C dropC(CH2)(10)SH (n = 2, 3) and CF3(CF2)(n)(CH2)(11)C dropC-C dropC(CH2)(10)SH (n = 9, 12) onto the surface of gold. The polymerization of the monolayers was initiated by UV irradiation and was monitored using resonance Raman spectroscopy. SAMs with short semi-fluorinated portions were found to polymerize more effectively than those with longer portions, indicating that steric factors become important with increasing perfluorinated chain length.