The analysis of flower volatiles requires special methods for their isolation with enrichment. Living flowers show a continuous change in their volatile profile that depends on intrinsic (genetic) and external (light, temperature, hydric stress) factors. Excised flowers suffer rapid deterioration and loss of volatiles. While industrial isolation methods for flower volatiles are well established, those at the laboratory-scale experience progressive development, in the search for higher sensitivity, reproducibility, and simplicity. This review covers the flower scent sampling methods most commonly employed during the last decade, and includes comments on their strengths and limitations. The strengths of headspace solid-phase microextraction (HS-SPME) for in vivo monitoring are emphasized with the examples of monitoring the circadian variation of Brugmansia suaveolens flower scent and of volatile aldehyde detection in flower scent using on-fiber derivatization.