An optimization of temperature, time, and extracting agent concentration of pectin extraction from sunflower heads using sodium citrate and nitric acid (SP‐SC and SP‐NA) was carried out. At optimal conditions, the yield of extraction with nitric acid (SPO‐NA) was twofold greater than the corresponding with sodium citrate (SPO‐SC) (14.3 versus 7.7%, respectively). Regarding pectin structure, the galacturonic acid (GalA) content in both, SPO‐SC and SPO‐NA, was similar (∼85%). However, SPO‐NA showed lower molecular weight (Mw) (88.9 kDa) and neutral sugar content (4%) than SPO‐SC (464 kDa, 9%), indicating that nitric acid deeply degraded pectin structure. These differences derived into dissimilar behavior in their technological functionality. SPO‐SC showed higher viscosity and better emulsifying capacity than SPO‐NA, although any of them were able to stabilize the oil/water emulsion. Both sunflower pectins formed gels with Ca²⁺ (75 mg/g of pectin) at pH 3.0. However, when sucrose was added, the gels formed by SP‐SC and 20% sucrose presented the same hardness as those of SP‐NA with 40% sucrose. These results suggest that the pectin extracted with sodium citrate, an eco‐friendly agent, could be a promising ingredient, with good thickening and gelling properties.