Coherent Raman scattering (CRS) spectroscopy is a powerful technique that can provide high-time and high-frequency resolution for investigation of various dynamical processes of molecules leading to chemical changes in the gas, liquid and solid phases. However, the strict demands on the femtosecond (fs) laser with either different carrier frequencies or broad bandwidth for building up the rovibrational coherence of molecules as well as on the high-intensity picosecond (ps) laser for inducing Raman transitions always make the CRS measurements difficult to conduct for standoff detections. In this chapter we propose a novel standoff CRS approach, where a broadband fs laser and a cavity-free picosecond air laser generated simultaneously by the filamentation of an 800-nm Ti:Sapphire laser are employed. We demonstrate that simultaneous standoff detections of coherent resonant and non-resonant Raman processes of molecules with high temporal resolution and high-frequency resolution are realized by this hybrid ps/fs laser. We further show that the optimization of the CRS signals can be realized by both the molecular rotational coupling and filamentary plasma grating. Finally, we present the applications of the CRS in probing the rovibrational wave packet dynamics of atmospheric species as well as in establishing ultrabroadband supercontinuum laser covering the UV and visible wavelength range.