Thermodynamic parameters for the dissolution of n-alkanes (C7-C11) and n-alcohols (C5-C9) under infinite dilution in the columnar and isotropic phases of a polypropylenimine dendrimer have been determined by inverse gas chromatography. Thermodynamic functions have been investigated as a function of the phase state of a mesogen, the length of alkyl chains of sorbates, and temperature. For the dissolution of low-molecular-mass organic compounds, a higher endothermic effect corresponds to a larger entropy factor with its positive deviation from ideality. The dominant effect of the entropy constituent of the Gibbs energy on the dissolution of sorbates in a high-molecular-mass LC solvent has been revealed. The Rohrschneider constants have been estimated for the stationary phase based on the dendrimer. The experimental data indicate the low polarity of the sorbent that is close to those of phenyl-containing siloxane phases.