We discuss a new technique of studying magnetic fields in diffuse astrophysical media, e.g. interstellar and intergalactic gas/plasma. This technique is based on the angular momentum alignment of atoms and ions in their ground or metastable states. The alignment reveals itself in terms of the polarization of the absorbed and emitted light. The corresponding studies of magnetic fields can be performed with multiband spectropolarimetry, from UV, optical, to IR/radio. A unique feature of these studies is that they can reveal the 3D orientation of magnetic field. We mention several cases of interplanetary, circumstellar and interstellar magnetic fields for which the studies of magnetic fields using ground state atomic alignment effect are promising.