Two new organic-inorganic hybrid crystals (C5H12NO)(4)Cd3Cl10 center dot 2H(2)O and (C5H12NO)(2)BiCl6 center dot H5O2 were synthesized by solution method, and their basic physical properties, including structures, thermal stability analysis, UV-Vis diffuse reflectance absorption spectra and photoluminescent characteristic were characterized. The two crystals both crystallize in same monoclinic crystal system, but different P2(1)/c and C2/c space group for (C5H12NO)(4)Cd3Cl10 center dot 2H(2)O and (C5H12NO)(2)BiCl6 center dot H5O2, respectively. Their infrared, Raman and mass spectrometry were measured, with related characteristic peaks were identified. The Raman peaks at 249 and 88 cm(-1) are ascribed to Cd-Cl stretching vibration and Cl-Cd-Cl deformation vibration, respectively. The mass spectra analysis confirm the existence of C5H12NO+ cation, [CdCl](+) and Na-(C5H12NO)(2)BiCl6 center dot H4O2. A phase transition peak that respectively located at 378 and 403 K for (C5H12NO)(4)Cd3Cl10 center dot 2H(2)O and (C5H12NO)(2)BiCl6 center dot H5O2 was detected by the synchronous thermal analysis, which is related with the loss of crystalline water in their structures. In addition, the maximum absorption peak at 230 and 240 nm, with corresponding band gap of 3.35 and 3.15 eV were fitted for (C5H12NO)(4)Cd3Cl10 center dot 2H(2)O and (C5H12NO)(2)BiCl6 center dot H5O2, respectively. Furthermore, (C5H12NO)(4)Cd3Cl10 center dot 2H(2)O features a bluish white emission with the peak centering at 496 nm when it was excited at 380 nm by a Xenon lamp. This work extends the catalog of organic-inorganic hybrid metal halides and presents the potential application of (C5H12NO)(4)Cd3Cl10 center dot 2H(2)O in optical field.