Metalorganic frameworks (MOFs) with cuprous-halide-aggregates have shown superiority as organic LED (OLED) and semiconductor materials, while engineering MOF flexibility by involving the expansion of cuprous aggregates remains a great challenge. In this particular work, a dissolutionrecrystallization structural transformation (DRST) with the dramatic growth of (CuI)-I-I aggregates, from 2D NJNU-100 to 3D NJNU-101 has been successfully realized. The unsaturated coordination nodes (2-positional nitrogen atoms) in NJNU-100 have been demonstrated to be the driven force for DRST to NJNU-101 via the formation of coordination bonds. The structural transformation process was irreversible and observed with optical microscopy and powder XRD. The expansion of CuII aggregates was also computational simulated accompanying with the rotation of the neutral tripodal TTTMB ligand (1,3,5-tris(1,2,4-triazol-1-ylmethyl)-2,4,6-trimethylbenzene) and the reduction of CuII to CuI. Moreover, the intermediate product NJNU-102 was captured by adding the planar molecular anthrancene to shut down the reaction, where only partial 2-positional nitrogen atoms coordinated to the aggregates and the anthrancene was oxidized to anthraquinone. NJNU-102 has further confirmed that DRST involved the breakage and recombination of coordination bonds and the electron transfer. NJNU-100 and NJNU-101 could be applied as semiconductor and OLED materials. This work has provided insights for crystal engineering, especially for the construction of the CuI(x)Xy aggregates, and illustrated that DRST could be controlled with a rational design (as the unsaturated coordination modes).