Total vaporization solid-phase microextraction (TV-SPME) is a type of extraction technique in which a specific solvent dissolves the analyte. Then a tiny amount of solvent is taken to the vial of SPME. Then, the solvent vaporizes in the SPME vial, and sampling is carried out on the headspace of the SPME fiber. As a result, the partitioning phase of the analyte between the headspace and liquid sample is omitted. The equilibrium phase remains the analyte partitioning between the headspace and SPME. TV-SPME was introduced in 2014 by Goodpaster to increase the recovery compared to the liquid injection method. This review discusses different aspects of TV-SPME, including its impact on sampling techniques, theoretical part, sampling procedure, and method optimization. Special attention was paid to its applications. A comprehensive literature study was conducted in the relevant databases to summarize the research work that has been done on this technique. In TV-SPME, the liquid samples completely vaporized and had a less matrix effect and better adsorption. This method needs no sample preparation, consumes less supply, and can be done automatically. Also, TV-SPME enables a cost-effective and efficient extraction for different matrixes. This review summarizes aspects related to TV-SPME.