[(CH 3 ) 3 P(CH 2 ) 2 OH] 2 Cd 3 (SCN) 8 ( 1 ) and [(CH 3 ) 3 P(CH 2 ) 2 OH]Cd(SCN) 3 ( 2 ) were obtained with completely different structures and properties under the same synthesis conditions. Compound 1 , showing green fluorescence, has a rare three-dimensional 4,6-connected fsh topology having (4 3 .6 3 ) 2 (4 6 .6 6 .8 3 ) Schläfli notation, while compound 2 with blue-violet phosphorescence displays a one-dimensional perovskite structure with an infinite {[Cd(SCN) 3 ] - } ∞ chain and exhibits both ferroelastic and dielectric switching characteristics.