Metal-organic frameworks (MOFs) containing face-to-face π-π interacting anthracene groups are promising photoresponsive materials because of their rich photophysical properties and their ability to undergo reversible [4+4] photocycloaddition reaction, but it is extremely challenging to obtain such materials. Herein, we propose a generalized method to accomplish photoresponsive MOFs by introducing anthracene pairs into the framework of the dianthracene-phosphonate-based MOFs by controlling the synthesis temperature. Compounds Dy2(ampH)2x(amp2H2)3-x(H2O)6∙4H2O [x = 0.01, Dy-70; x = 0.02, Dy-80; x = 0.037, Dy-90; amp2H4 = pre-photodimerized 9-anthracenemethylphosphonic acid (ampH2)] were obtained by the reaction of DyCl3 and amp2H4 in water at 70, 80, and 90 °C, respectively. They all show excimer emission of paired anthracenes at ca. 555 nm. Detailed studies of Dy-90 have shown that it undergoes a reversible photodimerization reaction under 365 nm and then 280 nm illumination, accompanied by luminescence changes. This property further enables Dy-90 to be used for optical anti-counterfeiting.