Today chemistry of materials and as such the ceramic field of research are addressed through more and more complex synthetic methodologies in order to optimize final material performances. The notion of complexity in chemical science is illustrated inhere through the concept of integrative chemistry. Particularly the integration between bi-liquid foams, sol-gel process, organo-silane functionnalization, lanthanides complexation and Pd heterogeneous nucleation is proposed as a non-exhaustive synthetic tool box to reach specific advanced ceramics. The first section is dealing with the synthesis of the first series of Si(HIPE) macrocellular foams where the oil volume fraction of the starting emulsion allows a nice tuning of the foams macroporosity. The second section is dealing with Europium complexation of diketone and malonamide hybrid Organo-Si(HIPE) leading to the Eu3+@Organo-Si(HIPE) luminescent foams, while the third part is dedicated to Pd heterogeneous nucleation within host hybrid foams. This last series of macrocellular ceramics are labeled Pd@Organo-Si(HIPE) which demonstrates good turn over number (TON) and turn over frequencies (TOF) when acting as supported catalysts for the Mizoroki-Heck coupling reactions. In the above mentioned foams the HIPE acronym is for High Internal Phase Emulsion.