Abstract Hollow fiber based liquid-phase microextraction technique (HF-LPME) was proposed in 1999 as an efficient alternative to the conventional sample preparation methods. Since its initiation, this technique have become increasingly popular due to their simplicity, low cost, possibility of for automation, and adaptability to a wide variety of sample matrices and analytes. The HF-LPME methods are mainly accomplished in two modes of two-phase and three-phase hollow fiber liquid-phase microextraction. This article covers the theoretical aspects and the developments of the two-phase hollow fiber liquid-phase microextraction technique as well as its applications to chemical analysis. Moreover, the pros and cons of this method and its advantages over other similar techniques are highlighted. More importantly, future directions and potential applications for a general implementation in routine/research laboratories are also prospected.