Analytical chemistry is one of the areas in chemistry that studies and uses methods and instruments to separate, identify and quantify target analyte/s from mixtures. It is widely used in different areas but not limited to pharmaceutical, agriculture, medical industry, clinical industry, radioimmunoassay, food and beverage industry, environmental and forensic analysis. Analysis starts with treatment of the sample and its preparation for further separation into its components. There is a wide choice of methods for sample pre-treatment and preparation for further analysis and the same applies to separation methods. The current trend is in the use of green analytical approaches in chemical separations. The term green analytical chemistry emerged from green chemistry in 2000. Scientists have developed advanced separation techniques which are environmentally friendlier analytical techniques applied to isolate and to enrich trace organic or inorganic pollutants from solid and aqueous samples where the amounts of organic solvents used in analytical laboratories are reduced by applying solvent less extraction, extraction using other types of solvent, assisted solvent extraction and miniaturized analytical systems and procedures. Waste prevention is a part of the decision process when choosing the proper analytical method i.e. analysis must be performed in a green way. In our attempt of ‘greening analytical chemistry’, we use solid phase-based extractions as a miniaturization of procedures in sample preparation. The extraction includes the use of dispersive solid-phase extractions, in-tube solid-phase micro-extraction, solid-phase micro-extraction, stir bar sorptive extraction, and magnetic solid-phase extraction in the miniaturization of procedures. The emphasis is on using newly developed sorbents based on silica, graphene, sporopollenin biopolymer and calixarenes for development of methods for analytes of interest from various types of samples. This presentation also include capillary electrophoresis separation as a green analytical separation method that promote the greening process through miniaturization of consumption of solvent volumes and deserve its mention in the separation of chiral drugs in combination with chemometrics approach.