Simultaneous dual post-synthetic modification was realised in multivariate isoreticular zinc 4,4'-biphenyldicarboxylate frameworks co-loaded with thermo-reactive allyloxy and propargyloxy groups. Radiative heating initiates dual cascade reactions, simultaneously changing both groups under the same conditions with preservation of framework topology and porosity. This work provides a new strategy to target multiple groups in shorter sequences for more efficient metal-organic framework post-synthetic modification.