By EPR spectroscopy, we have developed a new method for determining the molecular orientation in a surface-stabilized liquid crystal (LC) cell, which includes a paramagnetic LC, (2S, 5S)-2,5-dimethyl-2-heptyloxyphenyl-5-[ 4-(4-octyloxybenzenecarbonyloxy)phenyl]pyrrolidine-1-oxy (1), whose spin source is fixed in the rigid core. For each phase of racemic [(+/-)] and enantiomerically enriched [(S,S)]1 in a surface-stabilized LC cell (4 Am thickness), the observed g-value profiles depending on the angle between the applied magnetic field and the cell plane were successfully simulated by the orientation models: (i) the LC molecule in the nematic (N) phase of (+/-)-1 freely rotates around the long axis, which is always parallel to the rubbing direction; (ii) the long axis of the freely rotating LC molecule in the chiral nematic (N*) phase of (S,S)-1 is always parallel to the cell plane but rotates in the plane to form a helical superstructure; and (iii) in the crystalline phase of (S,S)-1, the molecular long axis forms a helical superstructure similar to that of the N* phase, but the molecule is fixed around the long axis so that the NO bond lies in the cell plane. Fitting the temperature profile of the g-value in the N phase of (+/-)-1 by use of the Haller equation, we determined the molecular g-values along the molecular long axis (g(parallel to M)) and short axis (g(perpendicular to M)), which were successfully reproduced by the use of the set of principal g-values of a similar nitroxide with consideration of the structure of the LC molecule optimized by Molecular Mechanics 3 (MM3).