Sample preparation is one of the most neglected areas of analytical chemistry, even though good sample preparation can be the critical factor in the success of an analytical method. Solid-phase extraction (SPE) has proven to be one of the most reliable methodologies for ensuring efficient sample extraction, pretreatment, and pre-concentration. However, the common sorbent materials used in solid-phase extraction lack specificity. Molecularly imprinted polymers (MIP) have established themselves as powerful sorbents for solid-phase extraction and overcome the lack of specificity seen for complex samples. These so-called plastic antibodies can be tailored and designed to recognize and bind to any analyte of choice. In this chapter, we aim to review the current state of the art in the use of MIPs as sorbent materials for solid-phase extraction. We will review the strategies and formats employed for MIPs used in solid-phase micro extraction (SPME). We will also discuss the advantages of using MIPs as sorbents in dispersive solid-phase extraction and how new multifunctional nanomaterials can be exploited for sample preparation. Finally, we briefly discuss the current commercial MIPs available on the market and the future direction of MIPs in sample preparation applications.