Since ambient mass spectrometry (AMS) has been proven to have low matrix effects and high salt tolerance, great efforts have been made for online coupling of several analytical techniques with AMS. These analytical techniques include gas chromatography (GC), liquid chromatography (LC), capillary electrophoresis (CE), surface plasmon resonance (SPR), and electrochemistry flow cells. Various ambient ionization sources, represented by desorption electrospray ionization (DESI) and direct analysis in real time (DART), have been utilized as interfaces for the online coupling techniques. Herein, we summarized the advances in these online coupling methods. Close attention has been paid to different interface setups for coupling, as well as limits of detection, tolerance to different matrices, and applications of these new coupling techniques.