On H-Si(111), monolayer assembly with 1-alkenes results in alkyl monolayers with a Si-C-C linkage to the silicon substrate, while 1-alkynes yield alkenyl monolayers with a Si-C=C linkage. To investigate the influence of the different linkage groups on the final monolayer structure, organic monolayers were prepared from 1-alkenes and 1-alkynes with chain lengths from C-12 to C-18, and the final monolayer structures were studied in detail by static water contact angles measurements, ellipsometry, attenuated total reflectance infrared (ATR-IR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). The thicknesses, tilt angles, and packing densities of the alkyl monolayers are in good agreement with literature values, whereas increased thicknesses, reduced tilt angles, and improved packing densities were observed for the alkenyl monolayers. Finally, the surface coverages for alkyl monolayers were determined to be 50-55% (in line with literature values), while those for the alkenyl monolayers increased with the chain length from 55% for C-12 to as high as 65% for C-18! The latter value is very close to the theoretical maximum of 69% obtainable on H-Si(111). Such enhanced monolayer quality and increased surface coverage of the alkenyl monolayers, in combination with the oxidation-inhibiting nature of the Si-C=C linkage, significantly increases the chance of successful implementation of organic monolayers on oxide-free silicon in molecular electronic and biosensor devices, especially in view of the importance of a defect-free monolayer structure and the corresponding stability of the monolayer-silicon interface.