The present invention provides a series of penta-substituted tetrahydropyrimidines with aggregation-induced emission (AIE) characteristics and preparation method and use thereof. The AIE penta-substituted tetrahydropyrimidines have structures shown as formula (I). R1 is selected from a group consisting of linear or branched alkyls and substituted alkyls. R2 and R4 is respectively selected from a group consisting of linear or branched alkyls, substituted alkyls, cycloalkyls, substituted cycloalkyls, aryls, substituted aryls, polycyclic aryls, substituted polycyclic aryls, heterocyclyls, substituted heterocyclyls, aromatic heterocyclyls and substituted aromatic heterocyclyls. R3 is selected from a group consisting of aryls, substituted aryls, polycyclic aryls, substituted polycyclic aryls, aromatic heterocyclyls and substituted aromatic heterocyclyls. The penta-substituted tetrahydropyrimidines can be prepared by multi-component reactions (MCR). There are 1˜3 aryls in the structure of the penta-substituted tetrahydropyrimidines. The penta-substituted tetrahydropyrimidines possess strong AIE properties and can be used for preparing organic electro-luminescence or photo-luminescence devices, or chemical and biological fluorescent sensors or probes.