C30 alkyl modified silica gels have attracted much attention because of their enhanced shape selectivity for various types of analytes, which for instance cannot be separated with conventional C8 and C18 stationary phases. Since the retention processes strongly depend on the nature of solvents and composition of the stationary phases, a FTIR study was conducted to evaluate the influence of solvents on the conformational order of the alkyl chains in C30 alkyl modified silica gels. Variable temperature IR measurements are carried out between 273 and 353 K in the presence of polar and nonpolar solvents. Information about the conformational behavior of the tethered alkyl chains is derived from the analysis of the symmetric and antisymmetric CH2 stretching band regions. Polar solvents show both enhanced conformational order and disorder of the alkyl chains - irrespective of temperature - when compared to dry C30 alkyl modified silica gels, while nonpolar solvents in general give rise to enhanced conformational disorder in the alkyl chain region. Moreover, for polar solvents a correlation exists between the stretching band position, reflecting alkyl chain conformational order, and the solvent solvatochromic parameter pi*. Finally, both partition and adsorption models are considered to play an important role for the solvent-alkyl chain interactions which in turn determines the conformational order of the alkyl chains and thus the chromatographic properties of these phases.