By assembling Cd2+ ions with two reported squaramide‐based ligands in solvothermal reaction condition, two new MOFs with the formulas Cd2(L1)(DMF)3 (sq‐Cd‐MOF‐1) (H4L1=5,5'‐((3,4‐dioxocylcobut‐1‐ene‐1,2‐diyl)bis(azanediyl) diisophthalic acid) and Cd(L2)(dpe) (sq‐Cd‐MOF‐2) (H2L2=3,3'‐((3,4‐dioxocyclobut‐1‐ene‐1,2‐diyl)bis(azanediyl)) dibenzoic acid, dpe=1,2‐di(pyridine‐4‐yl)ethane) are obtained. The MOFs are characterized by elemental analysis, IR, TGA, single‐crystal X‐ray diffraction, and PXRD. X‐ray data analysis reveals that sq‐Cd‐MOF‐1 possesses a new three‐dimensional framework with one dimension narrow apertures, while the structure of sq‐Cd‐MOF‐2 contains a novel ring‐ring connecting chain‐based double layer, as a two‐dimensional MOF. sq‐Cd‐MOF‐2 maintains high porosity via the packing of these layers. More importantly, reversible crystal to crystal transformation between sq‐Cd‐MOF‐2 and its activated state (sq‐Cd‐MOF‐2ac) is observed, triggered by the solvent in the pores. Michael addition reaction of the derivatives of β‐nitrostyrene and acetylacetone demonstrates that sq‐Cd‐MOF‐2 as a heterogeneous catalyst exhibits excellent catalytic capacity and stability. These results are useful for developing research on 2D soft MOFs and their potential application. [ABSTRACT FROM AUTHOR]