Membrane distillation (MD) is widely applied to desalination and wastewater treatment processes owing to its low operating pressure, superior rejection efficiency, and low membrane fouling. However, in addition to membrane fouling, MD suffers from temperature polarization (TP). In this study, gold nanoparticles (GNPs) were embedded in MD membranes to improve MD performance through the photothermal effect. Two different techniques (electrospinning and electrospraying) were used to fabricate the photothermal layer and systemically compared. Surface layers with different structures were formed. When irradiated with a continuous 808 nm laser (2 W), the TP coefficient ratios of the two different GNP/PVDF membranes obtained using electrospinning (5.7–8.0 %) and electrospraying (8.2–9.9 %) were higher than that of the virgin PVDF membrane (1.1–3.1 %). Furthermore, with laser irradiation, the organic fouling factors of the GNP-PVDF membranes fabricated via electrospinning and electrospraying decreased from 12.1 ± 3.4 to 9.2 ± 1.4 % and from 48.8 ± 0.5 to 18.3 ± 3.4 %, respectively. Therefore, this study provides a guideline for selecting the appropriate technique for fabricating the photothermal layer on electrospun photothermal MD membranes.