Cardiovascular diseases are the leading cause of death in the world and one of the major risk factors for their development is considered hyperlipidemia. Statins are most commonly used drugs in the treatment of hyperlipidemia, and are one of the most often prescribed drugs in general. Statins act by competitively inhibiting HMG-CoA reductase, the rate limiting enzyme in the cholesterol biosynthesis. Not all statins have official pharmacopoeia monographs, so new analytical methods for their identification and determination in active pharmaceutical ingredients and finished drug products are highly required. Statin therapy is long-term and they are used on daily basis, so their purity assessment is of great importance. Hence, development of selective and sensitive methods for characterization, identification and determination of their impurities is indispensable. Red fermented rice contatins 14 monacolins with hypolipemic effect, and the most important one is monacolin K, also known as lovastatin. There are numerous dietary supplements containing red fermented rice on the market. Unfortunately the relevant national agencies around the world warn of dietary supplements' poor quality and the need for their increased supervision and regular inspection. Therefore, the aim of this research was to develop new, fast, selective, sensitive, precise and accurate analytical methods for the identification and determination of statins, characterization and quantification of atorvastatins impurities, which is the most commonly used statin drug, and determination of active and toxic ingredients in red fermented rice. Highly sophisticated analytical techniques were used: capillary electrophoresis (CE), high performance liquid chromatography (HPLC) and mass spectrometry (MS). In total 6 new analytical methods were developed, validated and successfully applied. The proposed CE method represents a universal fast analytical method for the analysis of any of the six statins registered in the European Union. The content of four atorvastatin impurities was determined and eight other impurities were structurally characterized and identified by HPLC-DAD-MSn method. The results of the red fermented rice products analysis indicated significant deviations in lovastatin content from declared values and among different batches. This suggests the need for tighter, more detailed and more frequent control in order to ensure effectiveness, safety and quality of these products.