We synthesized and isolated two paramagnetic metallofullerenes of La@C-72 and Y@C-72 with different fullerene cages, which were characterized by electron paramagnetic resonance (EPR) spectroscopy and theoretical calculations. DFT calculations disclosed two possible isomers of La/Y@C-72 with C-72-C-2 and C-72-C-2, cages, both of which have similar thermodynamic stability and one pair of fused pentagons. Their paramagnetic properties were then studied by EPR spectroscopy, and the obtained EPR signals were analyzed with very different hyperfine coupling constants, revealing distinct electron spin distributions for these two species. Furthermore, the experimental coupling constants were compared with those of calculated coupling constants, and comparison results revealed that the produced La@C-72 has a C-72-C-2v cage and Y@C-72 has a C-72-C-2 cage. These studies illustrate that the electron spin can be used as a probe to identify metallofullerene structure due to the susceptibility of spin-metal couplings. The successful isolation and characterizations of La@C-72 and Y@C-72 with such a small C-72 cage reveal their stability that is important for application as paramagnetic molecule materials.