Abstract: The silver nitrate-silica gel separation technique as a kind of complexation chromatography is mostly used for separation and purification of unsaturated compounds. Compared with regular silica gel column chromatography, silver nitrate-silica gel separation technique has the advantage of separating geometric isomers of insect pheromones, such as alkenes, unsaturated alcohols, aldehydes, and esters. This review introduced the advantages, routine operational approach, and factors influencing the effectiveness of silver nitrate-silica gel separation technique, and further summarized its application in insect pheromone research and the structural features of insect pheromone applicable to this separation technique. This review can provide theoretical guidance on efficient and practical separation of insect pheromone components.