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While many photoresponsive metal‒organic frameworks (MOFs) have been reported to date, finding applications in several technologically relevant fields such as photocatalysis, sensors, and light‐emitting devices, significantly scarcer are the reports addressing the relationship between the MOFs emissive features and their crystalline domain size (i.e., micro‐ and nano‐sized materials). Herein, a valuable contribution is offered to this issue which consists of the use of reticular chemistry to prepare a Zr‐MOF featuring spatially separated tetracarboxylated‐functionalized perylenes as ligand. Single crystal X‐ray analysis of such Zr‐MOF revealed the formation of micro‐ and meso‐porous channels. The perylene‐based Zr‐MOF exhibited notable optoelectronic features, including a relatively small optical bandgap of 1.82 eV and emission features different from that of the constituting perylene ligand in the solid state. Additionally, local probe techniques are used to unveil the emission properties of isolated Zr‐MOF crystals. Space‐ and time‐resolved fluorescence studies revealed a strong dependence of the emissive features of the Zr‐MOF, both in terms of its intensity and lifetime, to the crystalline domain size. [ABSTRACT FROM AUTHOR]