A fulleropyrrolidine bearing a nitroxide free radical has been inserted into single-walled carbon nanotubes with the aid of supercritical CO2. Thanks to the encapsulated paramagnetic probes, it has been possible to detect and characterize the resulting peapod-like structure through electron paramagnetic resonance (EPR) spectroscopy. In particular, the analysis of spectral parameters derived from extensive EPR studies has elucidated the orientation and the residual rotational dynamics of the molecules embedded in the nanotubes. A limited anisotropic rotational freedom of the encapsulated fullerene nitroxide reveals a rather strong interaction of the probe with the surrounding nanotube walls. The interaction seems to involve the fullerene cage (as confirmed by Raman spectroscopy) and not the nitroxide moiety, whose EPR spectral characteristics, such as the isotropic hyperfine constant and the g-tensor, remain unaltered after encapsulation.