Isosorbide and isomannide are polycondensed in solution with trimesoyl chloride at a concentration of 0.06 mol L-1 for the synthesis of cyclic and multicyclic polyesters. The feed ratio diol/trimesoyl chloride is varied from 1.0/1.0 to 1.6/1.0. As all obtained polyesters prove insoluble, innovative solvent-free matrix assisted laser desorption ionization time-of-flight mass spectrometry (MALDI ToF MS) is performed for their characterization. The influence of the stereochemistry is shown to be of great importance for the cyclization trend. Both isosorbide and isomannide lead mainly to cyclic and multicyclic structures at a feed ratio of 1.0/1.0 and 1.1/1.0. Isomannide gives higher fractions of multicyclic structures. The products are characterized by complementary techniques such as C-13 cross polarization magic angle spinning nuclear magnetic resonance (C-13 CP-MAS NMR) and differential scanning calorimetry measurements. Application as a cryptands for the uptake of metal ions in aqueous media is followed by inductively coupled plasma atomic emission spectroscopy (ICP AES) analysis and reveal efficient toward large range of metals with tunable selectivity depending on the starting diol.