Paper chromatography and its various techniques for early detection of the molecules of the interest play a very important role in separation sciences. Qualitative analysis is major forte of paper chromatography where paper (cellulose) acts as stationary phase and solvent behaves as mobile phase. Different mobile phases like isopropanol-ammonia-water (9:1:2), n-butanol-acetic acid-water (4:1:5), phenol saturated with water, and various stationary phases like water, formamide, dimethyl formamide, and phenoxy ethanol are in vogue in chromatography. Pesticide residues can be detected by paper chromatography where paper act only as support for an immobile solvent, and the compound of the interest are separated by partitioning between mobile solvent on the paper and mobile solvent through the paper. Selection of the solvent and detection techniques are two major determinants for pesticide quantification as some of the pesticides are hydrophilic and some are hydrophobic one. Although mass spectrometry techniques have replaced not only paper chromatography but also HPLC and GC techniques, but paper chromatography plays a pivotal role in its early evolutionary trend in separation sciences.