A metal-organic framework Cu-2(BPDC)(2)(BPY) was synthesized and used as a heterogeneous catalyst for the copper-catalyzed A(3) reaction of tetrahydroisoquinoline, aldehydes, and alkynes to form C1-alkynylated tetrahydroisoquinolines. High regioselectivity to the endo-yne-product was achieved, with more than 99% of 2-benzyl-1-(phenylethynyl)-1,2,3,4-tetrahydroisoquinoline and less than 1% of 2-(1,3-diphenylprop-2-ynyl)-1,2,3,4-tetrahydroisoquinoline, being observed in the product mixture. The Cu-2(BPDC)(2)(BPY) also exhibited higher catalytic activity for the transformation than that of other Cu-MOFs such as Cu(BDC), Cu-2(BDC)(2)(BPY), Cu-2(EDB)(2)(BPY), Cu-3(BTC)(2) and Cu-2(BDC)(2)(DABCO). No product was detected for the reaction using other MOFs including Mn(BDC), Co-MOF-74, Zn-IRMOF-61, and Ni-2(BDC)(2)(DABCO). The Cu-2(BPDC)(2)(BPY) catalyst could be recovered and reused several times without a significant degradation in catalytic activity. (C) 2015 Elsevier B.V. All rights reserved.