Synthesizing 2D metal–organic frameworks (2D MOFs) in high yields and rational tailoring of the properties in a predictable manner for specific applications is extremely challenging. Now, a series of porphyrin‐based 2D lanthanide MOFs (Ln‐TCPP, Ln=Ce, Sm, Eu, Tb, Yb, TCPP=tetrakis(4‐carboxyphenyl) porphyrin) with different thickness were successfully prepared in a household microwave oven. The as‐prepared 2D Ln‐TCPP nanosheets showed thickness‐dependent photocatalytic performances towards photooxidation of 1,5‐dihydroxynaphthalene (1,5‐DHN) to synthesize juglone. Particularly, the Yb‐TCPP displayed outstanding photodynamic activity to generate O2− and 1O2. This work not only provides fundamental insights into structure designing and property tailoring of 2D MOFs nanosheets, but also pave a new way to improve the photocatalytic performance.

Synthesizing 2D metal–organic frameworks (2D MOFs) in high yields and rational tailoring of the properties in a predictable manner for specific applications is extremely challenging. Now, a series of porphyrin‐based 2D lanthanide MOFs (Ln‐TCPP, Ln=Ce, Sm, Eu, Tb, Yb, TCPP=tetrakis(4‐carboxyphenyl) porphyrin) with different thickness were successfully prepared in a household microwave oven. The as‐prepared 2D Ln‐TCPP nanosheets showed thickness‐dependent photocatalytic performances towards photooxidation of 1,5‐dihydroxynaphthalene (1,5‐DHN) to synthesize juglone. Particularly, the Yb‐TCPP displayed outstanding photodynamic activity to generate O2− and 1O2. This work not only provides fundamental insights into structure designing and property tailoring of 2D MOFs nanosheets, but also pave a new way to improve the photocatalytic performance.