A 3D supramolecular polymer based on calix[5]arene tethered poly(p-phenyleneethynylene) with a complementary porphyrin endowed with alkanediyldiammonium functions is prepared in solution but collapses when transferred to a chemically inert solid matrix forming a dispersion of de-phasing porphyrin aggregates. We found that a short thermal shock induces the de-aggregation of the porphyrin aggregates, and a partial restoration of the original 3D-supramolecular architecture.