Simplifying tedious sample preparation procedures to improve analysis efficiency is a major challenge in contemporary analytical chemistry. Solid phase microextraction (SPME), a technology developed for rapid sample pretreatment, has flexibility in design, geometry, and calibration strategies, which makes it a useful tool in a variety of fields, especially environmental and life sciences. Therefore, it is important to study the coupling between the microfluidic electrospray ionization (ESI) chip integrated with the solid phase microextraction (SPME) module and the electrospray mass spectrometer (MS). In our previous work, we designed a solid phase microextraction (SPME) module on a microfluidic chip through geometric design. However, automation and calibration methods for the extraction process remain unresolved in the SPME on-chip domain, which will lead to faster and more accurate results. This paper discusses the necessity to design a micromixer structure that can produce different elution conditions on the microfluidic chip. By calculating the channel resistances, the microfluidic chip's integrated module with the micromixer, SPME, and ESI emitters optimize the geometry structure. We propose the annular channel for SPME to perform the resistances balance of the entire chip. Finally, for SPME on a single chip, this work provides a quantitation calibration method to describe the distribution of the analytes between the sample and the extraction phase before reaching the adsorption equilibrium.