1,3,5-Tris(4-fluorobenzoyl)benzene (TFBB) and 2,6,4′-trifluorobenzophenone (TFB) were polycondensed with isosorbide and isomanide. All polycondensations were performed in a mixture of dimethyl sulfoxide and toluene with potassium carbonate as promotor. Optimal concentration to avoid gelation was set at 0.06 mol L−1. The different cyclization tendencies on the basis of monomers conformations are discussed. In the TFB series, the feed ratio isosorbide/TFB was varied from 1.0:1.0 to 1.5:1.0. A majority of linear and hyperbranched species were identified as main reaction products by matrix-assisted laser desorption/ionization-time-of-flight mass spectrometry regardless of the diol with slight cyclization tendency for isomannide. When TFBB was polycondensed with isosorbide, the cyclization tendency was significantly improved. The products obtained at a feed ratio of 1.41/1.0 and 1.51/1.0 were rich in cyclic and multicyclic species. More interesting results were obtained from the polycondensation of TFBB and isomannide, giving rise majoritarily to cyclic, bicyclic, and multicyclic species. Differential scanning calorimetric measurements indicated high glass transition temperature (around 200°C).