Photochromism is an important strategy for realizing reversible light-controllable fluorescence switching. In spite of several reports on fluorescence switching via a photochromic process, the success of photochromic multimetallic complexes reversibly showing fluorescence switching in the solid or crystalline state has been limited for their application importance. Here, we report a photoswitchable near-infrared (NIR) fluorescence based on photochromism in the azo-label 3d/4f heterometal-organic rhomboids, azo-Zn(2)Ln(2) (Ln = Eu (1), Yb (2), and Er (3)), in the crystalline state. An individual metallorhomboid contains up to four azobenzene fragments, which is prepared via the three-component assembly of a trans-azobenzenegrafted multifunctional ligand, and 3d and 4f metal ions. The photoisomerization quantum yields of azo-Zn(2)Ln(2) complexes can be retained or even higher when compared to the free ligand due to the modification of electronic structure. The impressive crystalline-state NIR luminescence is observed for the complexes of azo-Zn2Yb2 (2) and azo-Zn2Er2 (3) at room temperature. Intriguingly, the switchable NIR luminescence can be effectively regulated by photochromism in the crystalline state. These features endow the self-assembly of the 3d/4f metallorhomboid with synergetic multifunctional behavior between photochromism and NIR luminescence.