We discuss the fine structure and spin dynamics of spin-3/2 centers associated with silicon vacancies in silicon carbide. The centers have optically addressable spin states which makes them highly promising for quantum technologies. The fine structure of the spin centers turns out to be highly sensitive to mechanical pressure, external magnetic and electric fields, temperature variation, etc., which can be utilized for efficient room-temperature sensing, particularly by purely optical means or through the optically detected magnetic resonance. We discuss the experimental achievements in magnetometry and thermometry based on the spin state mixing at level anticrossings in an external magnetic field and the underlying microscopic mechanisms. We also discuss spin fluctuations in an ensemble of vacancies caused by interaction with environment.