Microwave and submillimeter molecular transition frequencies between nearly degenerated rotational levels, tunneling transitions, and mixed tunneling-rotational transitions show an extremely high sensitivity to the values of the fine-structure constant, α, and the electron-to-proton mass ratio, μ. This review summarizes the theoretical background on quantum-mechanical calculations of the sensitivity coefficients of such transitions to tiny changes in α and μ for a number of molecules which are usually observed in Galactic and extragalactic sources, and discusses the possibility of testing the space- and time-invariance of fundamental constants through comparison between precise laboratory measurements of the molecular rest frequencies and their astronomical counterparts. In particular, diatomic radicals CH, OH, NH+, and a linear polyatomic radical C3H in Π electronic ground state, polyatomic molecules NH3, ND3, NH2D, NHD2, H2O2, H3O+, CH3OH, and CH3NH2 in their tunneling and tunneling-rotational modes are considered. It is shown that sensitivity coefficients strongly depend on the quantum numbers of the corresponding transitions. This can be used for astrophysical tests of Einstein's Equivalence Principle all over the Universe at an unprecedented level of sensitivity of , which is a limit three to two orders of magnitude lower as compared to the current constraints on cosmological variations of α and μ: , .