We present a thoroughgoing electron paramagnetic resonance investigation of polydopamine (PDA) radicals using multiple electron paramagnetic resonance techniques at the W-band (94 GHz), electron nuclear double resonance at the Q-band (34 GHz), spin relaxation, and continuous wave measurements at the X-band (9 GHz). The analysis proves the existence of two distinct paramagnetic species in the PDA structure. One of the two radical species is characterized by a long spin-lattice T1 relaxation time equal to 46.9 ms at 5 K and is assigned to the radical center on oxygen. The obtained data revealed that the paramagnetic species exhibit different electron spin relaxation behaviors due to different couplings to local phonons, which confirm spatial distancing between two radical types. Our results shed new light on the radical structure of PDA, which is of great importance in the application of PDA in materials science and biomedicine and allows us to better understand the properties of these materials and predict their future applications.