A method for the determination of six water-soluble vitamins based on capillary electrophoresis (CE) operated in micellar mode was developed. Thiamine hydrochloride (vitamin B1), riboflavin (vitamin B2), pyridoxine hydrochloride (vitamin B6), pantothenic acid (vitamin B5), nicotinamide (vitamin B3), and cobalamin (Vitamin B12) could be separated in a single run. All CE parameters such as buffer composition and operation temperature were optimized in order to achieve better separation. Relative standard deviations (RSDs) of the described method ranged from 1.08 to 3.68% (intra-day precision) and 1.26 to 3.35% (inter-day precision). The method was then used for measuring various soft drinks and vitamin supplements directly without any step of sample cleanup. The determination of niacin was successful for all samples tested, reaching recoveries near 100%. Riboflavin and pyridoxine were quantified successfully in some but not all samples. Therefore, an evaluation on a case-by-case basis is mandatory. When applicable, this method provides a fast, accurate, simple, and inexpensive way to quantify selected vitamins, and is therefore well suited for routine analysis in soft drink industry.