The monomeric ether-phosphine ligands (CH3O)3Si(CH2)3(Ph)PCH2D [D = CH2OCH3 (1a), tetrahydrofuryl (1b), and 1,4-dioxanyl (1c)] and their P-coordinated trimethoxysilyl- (T-) functionalized ruthenium(II) complexes HRuCl(CO)(P approximately 0)3 (3a-c) were copolymerized with variable amounts of Si(OEt)4 (Q elements) under various sol-gel conditions to give the polysiloxane-bound ether-phosphine ligands 1a’(Q(n))x-1c’(Q(n))x and (ether-phosphine)ruthenium-(II) complexes 3a’(Q(n))x-3c’(Q(n))x, [P approximately O : eta1-P-coordinated; (Q(n))x : x = number of cocondensated Q type silicon atoms, n = 2-4, the number of Si-O-Si bonds]. Detailed P-31 and C-13 spin-lattice relaxation time studies (T1P, T1C, T1rhoH) show that the noncomplexed ether-phosphine ligands strongly increase their mobilities in the gels at rising temperatures, while the coordinated ligands in the complexes are less mobile and rigidly bound to ruthenium. Solid-state Si-29 NMR spectroscopy has been used to determine the relative amounts of the T and Q silyl species and the degree of condensation. Moreover, the molecular mixing of the copolymerized components in the samples has been investigated and the transition to the silica gel attached system 3c’-silica gel elucidated. The materials, obtained by the different sol-gel variants, differ in their amount of Q species, degree of condensation, and their particle sizes, which strongly influence their catalytic behavior. Although the BET surfaces are in the range of the external surface of the gels, a high catalytic activity has been found when small particle sizes have been combined with a low content of Q silicon moieties. This can be traced back to a high flexibility of such materials, which allows swelling and an increase of the surface during hydrogenation of n-butyraldehyde to butanol within the gel. The undesired tendency to form highly swollen gels in alcohols after catalysis, which complicate the separation of the catalysts from the products, has been suppressed without loss of catalytic activity by the use of a modified matrix containing small amounts of insoluble ionic magnesium silicates. Constant elemental analyses of this material after three identical catalytic runs demonstrate the. possibilities of this system, which unifies the advantages of organic and inorganic polymer networks and those of homogeneous and heterogeneous catalyses.