High harmonic generation (HHG) has important applications in attosecond science, such as generating attosecond pulses and probing the structure and the electron dynamics of atoms and molecules with attosecond resolution. Different from symmetric cases, because of symmetry breaking, asymmetric molecules can emit both odd-order and even-order harmonics in strong single-color laser fields. Ultrafast probing of polar molecules with HHG is a hot issue in recent years, as polar molecules are generally very active in chemical reactions. With dividing the HHG signal into odd and even parts, recent studies have shown that odd and even harmonics from asymmetric molecules have different properties in frequency domain. To explain this typical difference, a theoretical model has been developed to describe the generation mechanism of odd versus even HHG from asymmetric molecules. It is shown that during the process of tunneling, the gerade component of the asymmetric orbital plays a dominating role and the contributions of the ungerade component can be neglected. Thereafter, the recombination of the rescattering electron with the gerade (ungerade) component of the asymmetric orbital mainly contributes to the emission of odd (even) harmonics. As a result, odd and even harmonics carry different information of the asymmetric system. Recently, it has been shown that the contributions of the ungerade component of asymmetric orbital to ionization are strongly suppressed due to the destructive intramolecular interference. This suppressing effect is general for strong-field ionization of polar molecules, implying that the theoretical model of odd-even HHG holds for a wide parameter region. These results open a new perspective for probing polar molecules with odd-even HHG. Specifically, when it is relatively difficult to read the information of the molecular structure or the electron dynamics through the whole harmonic spectrum of asymmetric molecules, one can extract the characteristic information of odd or even harmonic separately, then this characteristic information can be integrated and inverted to get the information of the whole asymmetric system. These discussions suggest ultrafast probing of asymmetric molecules with odd-even high-harmonic spectroscopy (HHS), where odd and even harmonics are treated independently. This idea of odd-even HHS and the theoretical model of odd-even HHG mentioned above have been widely used in ultrafast probing of asymmetric molecules in theoretical studies. For example, it has been shown that odd-even HHS and this theoretical model can be used to reconstruct the asymmetric molecular orbital, probe the nuclear dynamics of polar molecules, calibrate the degree of orientation of asymmetric molecules, and probe the structure of multi-center molecules, etc. Experimentally, the idea of odd-even HHS has also been widely used in probing the structure and the electron dynamics of polar molecules. In particular, this theoretical model of odd-even HHG has also been used in probing the shape resonance and charge transport of asymmetric molecules in experiments. In addition, theoretical studies based on the first-principle calculations have also shown the applicability of this theoretical model of odd-even HHG, which provides the theoretical tool for the present odd-even HHS. The research and development of odd-even HHS plays an important role in promoting the application of HHG in attosecond science and chemical reactions.