The behavior of isolated poly(epsilon-caprolactone) (PEC) chains confined to the narrow channels of their crystalline inclusion compound (IC) with urea is contrasted with the behavior of PEC chains observed in bulk, semicrystalline samples. DSC observations of bulk and IC-recovered PEC samples revealed that PEC recovered from PEC-U-IC via extraction with a nonsolvent for PEC produces crystals that melt 6 degrees C higher than PEC samples recrystallized from solution or the melt. Presumably an extended chain morphology results when PEC crystals are obtained from the collapse of PEC-U-IC. FTIR and CPMAS/DD C-13 NMR observations both point to similar extended, nearly all-trans conformations for PEC chains in PEC-U-IC and in the bulk. Quantitative observations by both techniques yield a molar stoichiometry of U/PEC = 4/1. Solid-state C-13 NMR observations show channel-bound PEC chains in PEC-U-IC have spin-lattice relaxation times (T-1) only 20-50% as long as those observed for bulk PEC samples. On the other hand, the Tl’s observed for the urea carbonyl carbons in PEC-U-IC and n-hexadecane-U-IC are nearly identical, though the included n-hexadecane chains are known to be considerably more mobile than the included PEC chains.