Micro-extraction techniques in sample preparation are gaining interest among analytical chemists as they comply with green analytical chemistry demands and ensure environmental protection and public safety. Savings in cost and time are considered as valuable benefits by using novel micro-extraction approaches in sample handling. Selectivity, sensitivity and lower detection limits are also included among the performance characteristics required to meet the legislation criteria. The target of this special issue is to present the state of art in microextraction sample preparation techniques. Modern, simple and efficient methods for preconcentration and separation are described for different analytes isolated from various matrices.