The structure, polarity and dynamics of radical microenvironment in some biological systems were determined by the method of spin label and probe at 2-mm waveband EPR. The hydrogen bond in radical complexes was found to be weaker at the temperature increase and at the sample wetting. The correlation of the radical complex type with the radical structure, its microenvironment, other parameters was found. It was shown, that the Brownian anisotropic diffusion is realized in inverted micelles, cellulose, other objects, whereas librative motion is characteristic for a cotton fibers. A more complete investigation of superslow anisotropic molecular motion was shown to be possible using the methods of steady-state saturation and saturation transfer at 2-mm waveband EPR. The method of macrospin probe for an investigation of low-viscous biological objects was elaborated.