Saffron, the dried red stigmas of Crocus sativus L. plant, is the most expensive spice in the world. It is highly valued not only for the color and flavor that exerts to various foods and drinks but also for its functional properties. Various classes of apocarotenoids such as crocetin sugar esters, picrocrocin and safranal are responsible for these characteristics. In the present review, the evolution of the methods proposed by the ISO standard for extraction and determination of saffron apocarotenoids since 1980 is presented in parallel to other approaches proposed by various scientists to overcome limitations of the standard. Moreover, the latest advances regarding applications of novel extraction techniques and powerful analytical tools that require limited or no sample preparation are critically discussed.