Abstract Molecularly imprinted polymers (MIPs) as materials with determined levels of selectivity and specificity for designated analytes have recently gained much attention in various application fields. However, with the growing adoption of green analytical chemistry (GAC) principles, it is essential to investigate the greenness of MIP synthesis and its subsequent application in sample preparation, as well as to evaluate the “green” nature of the developed analytical methodologies, such as dispersive solid-phase microextraction (DSPME). Accordingly, the main objective of this research was to evaluate the greenness of MIP-based glycidyl methacrylate synthesis and MIP use as a DSPME sorbent prior to high-performance liquid chromatography with mass spectrometry (HPLC-MS). The green perspective of MIP-DSPME prior to HPLC-MS was investigated using various analytical metric tools such as the Analytical Eco-Scale, the Green Analytical Procedure Index, and Analytical GREEnness (AGREE). Since these analytical tools are not fully implementable for the assessment of the greenness of the MIP synthesis, some alternative approaches were used to optimize the synthesis parameters to make the MIP DSPME sorbent as close as possible to the GAC principles. The calculated AGREE score (0.62) and 91 points in the Analytical Eco-Scale for the proposed DSPME technique using MIP indicated a high level of greenness.