The arrangement of Tetrathiafulvalene (TTF) plays a critical role in modulating the photocurrent responses of MOFs. In this work, employing m-H4-TTFTB as the building block and Cd as the metal center, two distinct MOF materials were selectively synthesized, and one MOF is different from the another one due to the incorporating of the (E)-1,2-di (pyridin-4-yl)ethene (BPE) unit. The MOF comprised solely of 3,3′,3″,3‴-([2,2′-bi (1,3-dithiolylidene)]-4,4′,5,5′-tetrayl)tetrabenzoic acid (m-H4-TTFTB) ligands showcased a 2D spatial arrangement. Differently, the introduction of the BPE unit facilitated the transition from a 2D to a 3D MOF architecture. The resulting 3D MOF exhibited an enhanced thermal stability compared to its 2D counterpart. Nevertheless, owing to the denser TTF arrangement demonstrated by the 2D MOF, its photoresponse performance also proved superior, approximately 1.2 times that of the Cd-BPE-m-TTFTB crystal.