Abstract: The present invention provides monolithic polymer matrices for the separation of bio-organic molecules by liquid chromatography. In one embodiment, the matrix is formed from a polymerization mixture including (i) a hydrophobic monomer, (ii) a crosslinking agent, and (iii) a porogenic solvent or mixture of porogenic components. The monolithic matrices of the invention are particularly useful for resolving polynucleotides (e.g., DNA and/or RNA) in samples by way of reversed-phase ion-pairing chromatography.