An electron paramagnetic resonance (EPR) study of 3,4-fulleropyrrolidine-2-spiro-4'-[2',2',6',6'-tetramethyl]piperidine-1'-oxyl (1) was performed on the photoexcited quartet state in toluene glass. The spectrum of the \S,Ms > = \3/2,+/- 3/2 >double left right arrow\3/2,+/- 1/2 > transitions was observed selectively by using a two-dimensional (2D) nutation method and analyzed with a spectral simulation in a randomly oriented system. A position of the nitroxide moiety was determined with respect to the zero-field splitting (zfs) axes of excited triplet fullerene (C-3(60)) by taking into account of the dipolar-dipolar interaction between the radical and C-3(60), the hyperfine coupling, the anisotropic g-value of the nitroxide radical, and the zfs of the C-3(60) moiety. It was found that none of the zfs axes of the C-3(60) moiety coincide with the local C-2 axis of the molecule which is defined by the position of addition. A symmetry of the electronic structure in C-3(60) is discussed on the basis of the result.