Interpenetrated multicomponent MIL-142(Sc) MOFs were synthesised using the planar tritopic (4,4′,4′′-(1,3,5-triazine-2,4,6-triyl)tribenzoate, TATB, or 4,4′,4′′-(pyridine-2,4,6-triyl)tribenzoate, PTB) and linear ditopic (1,4-benzenedicarboxylate, BDC, or 2-amino or 2-nitro-1,4-benzenedicarboxylate (NH2- or NO2-BDC) linkers. Structure solution of the MIL-142(Sc)-TATB series from single crystal X-ray diffraction in space group Rm reveals regioselective ordering of bulky NO2 groups in MIL-142(Sc)-TATB-NO2. Use of 1,3,5-benzenetribenzoate (BTB) favours instead the mesoporous Sc-BTB, the PTB analogue of which forms in the absence of BDC. The materials are highly porous: MIL-142(Sc)-TATB-BDC has a pore volume of 0.70 cm3 g−1.