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 (approximate to 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.