Corrosion inhibitors are amines-based which are added to the crude oil streams to prevent the pipelines from the corrosive attacks of oxygen by forming a film that coats the internal surface of a pipeline. Amines residuals should be monitored in the system and this is classically done by liquid-liquid extraction (LLE) of amines followed by colorimetric determination using spectrophotometry.In this work solid phase microextraction (SPME) a novel extraction technique that uses no solvent was used as a sample preparation technique to isolate the amines from the complex sample matrix and gas chromatography (GC) system was used for separation and quantification of amines. Flow-through system was used to simulate the process of flowing streams in pipelines during oil production. A method was developed to determine amines residuals at the lowest detection limit possible at the optimized conditions such as solution pH and sand contents. It was found that residuals can be determined as low as 1 ng/mL using GC/FID system. This method was developed in the lab using the flow-through system and synthesized waste water.Also in-fiber kinetic calibration was proposed to be used to calculate the concentration of amines in the field by applying the dominant desorption approach. This will significantly shorten the extraction time of amines which will make the method suitable for on-site analyses. This requires preloading the SPME fiber with a standard desorb it in the flowing streams and the remaining standard is desorbed in the GC for separation and quantification.This method is environmental friendly technique that will minimize the use of hazardous solvents and hence the need for the proper disposal of them. Also it does not require pretreatment steps of samples and many reagents to be used in the extraction processes of amines residuals. Finally it will provide more precise results in timely manner for better and quicker actions.