Di- and tetraphosphines with rigid phenyl-, bilphenyl-, and tetraphenylstannane, -silane, and -methane scaffolds, and various substituents F, have been synthesized and immobilized via triethoxysilane-propagated formation of one or two surface-bound phosphonium moieties. The remaining phosphine groups can be coordinated to metal complexes. All the detective work and proof is done by solid-state NMR spectroscopy.