This study attempts to combine the advantages of microcolumn high-performance liquid chromatography (micro-HPLC) with those of post-column photochemical derivatization in barbiturate analysis. Some barbiturates are photochemically unstable, leading to photoproducts that show maximum absorption at 270 nm and not the typical one at approximately 220 nm. For this purpose, a laboratory-built photoreactor has been developed to work with micro-HPLC instruments. Its performance is satisfactory in the forensic analysis of barbiturates.