The self-assembled monolayer formation of a series of thiophene dendron thiols with different generations and alkyl chain lengths onto gold surfaces is studied. Average film thicknesses and dielectric constants were calculated from SPR using a two-subphase differential method. The in situ adsorption of the thiophene dendron thiols was monitored by SPR kinetics measurements and fitted using an empirical three-step model. Electrochemical redox molecular probing experiments provided additional insight into surface coverage, which showed different abilities to block electron transfer at the monolayer/electrode interfaces. The surface coverage of the films was also estimated by QCM measurements and supported by static WCA measurements.