Biomedical analyses of drugs and their metabolites are important in new drug development, therapeutic drug monitoring and forensic toxicology. In these analyses, sample preparation is very important to isolate target compounds from complex biological matrices and markedly influences the reliability and accuracy of determination. SPME is a simple and convenient sample preparation technique that has enabled automation, miniaturization and high-throughput performance. This article focuses on current developments, their biomedical applications and future trends with emphasis on new extraction devices using selective polymer coating materials in novel SPME techniques, including fiber SPME, in-tube SPME and related techniques.