To benefit from the large capacity gain advantages offered by lithium-induced electrochemical alloying and to overcome poor kinetics, a novel concept to tackle such issues by using porous hierarchical microspheres with an interconnected network of nanoplate building blocks, has been introduced and demonstrated with Sn1.0P1.17O4.72 glass as an example. Such desired three-dimensional microarchitectures with exciting nanosize effects can be exploited to fabricate next generation of lithium-ion batteries where outstanding rate capability and sustained reversible capacity are achieved.