The introduction of highly volatile fragrances within polymeric nano-scaled fibers is a promising route for efficient and simple encapsulation of temperature-sensitive materials. This work describes the investigation of selected parameters influencing the electrospinning of emulsions of poly(vinyl alcohol) (PVA) and (R)-(+) limonene or hexadecane. Thereby the influence of environmental parameters such as temperature and relative humidity on the fiber structure and encapsulation efficiency (EE) of the fragrance is demonstrated. For that purpose, the electrospinning process was carried out in a climatic cabin in which temperature and relative humidity were controlled. Studied temperatures ranged from 8 to 24 °C and relative humidity varied between 55 and 85 %. The influence of temperature was dependent on the PVA concentration in the emulsion. The relative humidity influenced both the obtained fiber morphology and fragrance EE to a higher extent than the temperature due to the hydrophilic nature of the PVA. This study is of importance when considering the use of emulsion electrospinning for encapsulation purposes.