Calibration of SPME by the injection of liquid standard solution is a common method for SPME quantitative analysis by gas chromatography. The feasibility of this calibration method relies on the assumption that sample transfer efficiencies are the same for both the liquid injection and the SPME fiber injection. Sample transfer efficiencies for liquid injection and SPME fiber injection were studied in this paper. The results showed that the sample transfer efficiency for liquid injection was affected by several factors, such as the dimensions of the liner, the presence of the wool, and the temperature of the injector. The sample transfer efficiency for SPME fiber injection was affected by the cross-sectional area of the space between the column and the liner, the carrier gas flow rate, and the length of the column inside the liner. An equation was proposed to estimate the sample loss rate for SPME injection. It was found that the use of a direct injection (DI) liner and program temperature vaporizing provides high sample transfer efficiencies, for both liquid injection and SPME fiber injection. When a common SPME straight liner is used, large outer diameter (o.d.) pre-column will help to achieve high sample transfer efficiency.