More than 80% of analysis time is spent on sample collection and sample preparation, so sample preparation is a critical part of the analytical process. Traditionally, liquid-liquid extraction was developed and employed to screen for general unknowns. However, solid-phase extraction (SPE) is becoming highly popular as an alternative, due to its simplicity and economy in terms of time and solvent. This review summarizes the current state of the art and the future prospects for green analytical chemistry with special emphasis on environment-friendly sample-preparation techniques based on the solid phase. We discuss in detail miniaturized SPE techniques, based on the most relevant, most representative and most recent scientific references.