Hierarchical porous architecture with interconnected trimodal micro-meso-macroporous systems constructed from uniform zeolite Zr-doped silicalite-1 nanocrystals has been prepared. The synthesis has been made by using glycerin as a reaction medium via a quasi-solid-state crystallization of hierarchically meso-macroporous zirconosilicate precursor under the effect of the structure directing agent TPAOH. The presence of glycerin is crucial in the synthesis systems to maintain the porous hierarchy. The pores inter-connectivity, Zr location in the framework, the acidity and the catalytic activity have been studied by laser-hyperpolarized Xe-129 NMR spectroscopy, UV-visible spectroscopy, temperature-programmed desorption of ammonia and the catalytic isopropylbenzene cracking probe reaction, respectively. The products possess well-defined macrochannels interconnected with mesopores located in the macropore walls, which in turn have been constructed from microporous MFI-type zeolite units. Xe-129 NMR study indicated that the hierarchically micro-, meso-, macro-pore systems are homogeneously distributed throughout the final materials and well interconnected, which is important for molecular diffusion. The TPD-NH3 investigation revealed that the hierarchically micro-meso-macroporous materials constructed from zeolite Zr-Silicalite-1 nanocrystals present strong acidity. (C) 2012 Elsevier Inc. All rights reserved.