According to scientists researches, conventional energy resources are exhausting. On the other hand, energy supply using fossil fuels leads to increase in greenhouse gas concentration and air pollution, both of which are world concerns. Therefore, many attempts have been devoted to harvest energy from green and renewable sources such as solar energy. In this regard, design and production of photothermal electrospun webs have drawn a great attention. This type of electrospun webs can convert solar energy to thermal energy. In this research work, nanocomposite webs composed of polystyrene (PS) fibers and silver nanoparticles (Ag ) are produced using electrospinning technique. The electrospun webs are characterized with respect to the photothermal properties. Ag are incorporated into the structure of electrospun fibers using two different methods: (1) addition of Ag with concentrations of 2, 4 and 6 wt.% (with respect to polymer weight) to the electrospinning solution (PS- Ag webs), (2) Electrospinning of solutions containing silver nitrate (AgNO3) and then reducing the Ag+ to Ag using sodium borohydride to produce Ag nanoparticles with concentrations of 2, 6, 15 and 18 wt.% (with respect to PS weight) within the structure of PS fibers (PS-AgNO3 webs). Investigation of the photothermal performance of produced webs showed that regardless of the web production method, the surface temperature of electrospun web is directly related to Ag concentration in the electrospinning solution and UV lamp power. Contrarily, by decreasing distance between UV lamp and web, the surface temperature of web increases. Furthermore, using AgNO3 yields to superior photothermal performance over the AG due to uniform distribution of Ag within the whole structure of electrospun fibers. In this regard, the maximum measured temperature on the surface of photothermal electrospun webs produced using Ag and AgNO3 was recorded as 41 and 78 oC, respectively. Additionally, measured water contact angles on the surface of PS-AgNO3 webs denote to the hydrophobicity of the produced webs, which is essential for applications such as photothermal membrane distillation. Overall, it can be said that the PS/Ag nanocomposite photothermal web produced using electrospinning of AgNO3-containing solution is a promising candidate for a variety of applications based on solar energy. Keywords: Photothermal web, Hydrophobic, Polystyrene, Silver, Electrospinning