Synthesis of layered materials exhibiting hierarchical porosity remains challenging, but nevertheless worthwhile because it turns such solids into functional materials with high specific surface area. Using a soft-templating strategy in combination with the incorporation of 8-fold coordinated Eu3+, self-assembly of self-supported layered double hydroxide (LDH) nanotubes has been achieved. Heteromorphic equimolar substitution of Al3+ by Eu3+ in Zn2+/Al3+ LDH solids intercalated with 1,3,5-benzenetricarboxylate anions (BTC) assists precipitation of the double hydroxide layers onto the convex surface of Pluronic® P-123 worm-like micelles, yielding multilayer cylinders of BTC-intercalated LDHs. Removal of the micellar template is easily achieved by liquid extraction with methanol, yielding a network of interconnected, well-defined, self-supported, multi-walled, hollow cylindrical nanotubes. Removal of Eu3+ from the synthesis disables formation of the nanotubular morphology, but still yields LDHs containing a network of embedded mesopores, resulting in a specific surface area that is 5-fold higher as compared to standard LDHs.