Aiming at modulating the packing density within functional self-assembled monolayers (SAMs), two azo-biphenyl derivatives AZO1 and AZO2 comprising a terminal sulfur anchor group have been designed and synthesized. While AZO1 allows for a coplanar arrangement of both biphenyl subunits, additional steric repulsion due to two methyl side groups attached to the footing biphenyl of AZO2 results in an increased intermolecular distance within the SAM, providing additional free volume. SAMs of both derivatives on gold and platinum substrates have been formed and thoroughly investigated by photoelectron (XPS) and near-edge absorption fine structure (NEXAFS) spectroscopy as well as cyclic voltammetry and scanning tunneling microscopy. These measurements confirmed the formation of tightly packed SAMs for AZO1, while AZO2 formed SAMs consisting of less organized and more loosely packed molecules. Optical investigations of both azo derivatives in solution as well as their SAMs displayed efficient photoisomerization in solution and in SAMs. Comparable maximal cis/trans ratios of ca. 0.9 have been observed in all cases upon irradiation at λ = 370 and 360 nm for AZO1 and AZO2, respectively. The thermally induced cis → trans back reaction on AZO1 was found to be slower by a factor of 3 in SAMs as compared to solution, while AZO2 displayed comparable rates of the back reaction in both environments. This behavior can be explained by the different nature of molecular isomerization in the two SAM systems: whereas the isomerization in AZO1 SAMs takes place in a highly coordinated, collective way and involves many adjacent molecules, AZO2 species behave rather individually even packed in SAMs, such that their isomerization process is similar in SAMs and in solutions.