A doubly interpenetrated Cu(II)‐organic framework with formula [{Cu2(L)2(4,4′‐bpdc)2(H2O)2} ⋅ 8H2O ⋅ CH3OH]α (1) (where, L=N2, N6‐di(pyridin‐4‐yl)naphthalene‐2,6‐dicarboxamide and 4,4′‐bpdc=[1,1′‐biphenyl]‐4,4′‐dicarboxylate ion) has been synthesized and characterized with the help of several spectroscopic and analytical techniques including single crystal X‐ray analysis. A single crystal X‐ray analysis reveals that 1 exhibit interpenetrated two‐dimensional sheet‐like structure containing elongated channels of cross‐section 11.09×31.22 Å2 along the a‐axis. Finally, 1 has been exploited as a heterogeneous catalyst for the ipso‐hydroxylation of arylboronic acids yielding up to 99 % of the respective phenolic product. Importantly, the catalyst can be reused for five successive cycles without having a significant loss in its catalytic efficiency.