This account presents the preparation, characterization, and applications of porous solgel materials with particular emphasis on non-siliceous oxide compositions and morphology control. The potential and versatility of innovative synthesis strategies that have been developed to broaden the range of achievable compositions and functionalities are briefly discussed. The synthesis approach involves polymerization-induced phase separation and concurrent solgel transition under well-controlled reactions conditions, producing monolithic gels with well-defined macroporous bicontinuous structures. By optimizing the template-free synthesis routes including the postgelation treatments, one can obtain non-siliceous monolithic materials with controllable macropores and mesopores. Promising results for chromatographic and optical applications are also demonstrated taking porous titania monoliths as a example.