Poly(vinyl chloride) (PVC) samples for the conformation and structural relaxation studies were prepared by freeze-extracting the solutions in various solvents and with varying concentrations. The partially disentangled PVC samples could be obtained by freeze-extracting very dilute PVC/tetrahydrofuran (THF) and PVC/dimethyl phthalate (DMP) solution (0.05 wt %), while the PVC sample remains in an entangled state after freeze-extracting the concentrated solutions in THF and in DMP. Surprisingly, the extent of interpenetration of PVC chain decreases, even in concentrated solution in dioctyl phthalate (DOP) (5 wt %), which is contrary to accepted theories. DSC and infrared spectroscopic studies showed that a higher ordered conformation could be achieved for the disentangled specimens recovered from concentrated solution in DOP than for the entangled samples prepared from THF and DMP. DSC heating curves showed strong and sharp endothermal peaks for the disentangled polymer after sub-Tg annealing. The structural relaxation behavior of the disentangled PVC freeze-extracted from DOP solutions is more predominant, which is in good agreement with the modeling predictions.