A natural low-methoxyl pectin (LAHP), was extracted with oxalic acid solution from dried heads of sunflower (Helianthus annuus L.). The single-factor experiments and response surface methodology (RSM) were used to optimize LAHP extraction conditions. The extraction yield of LAHP was 18.83 ± 0.21%, and the uronic acid content was 85.43 ± 2.9% obtained under the optimized conditions (temperature of 96 °C, time of 1.64 h, oxalic acid concentration of 0.21%). Experimentally obtained values were in agreement with those predicted by RSM model, indicating suitability of the employed model and the success of RSM in optimizing the extraction conditions. LAHP has been characterized by ash content, degree of esterification (DE), galacturonic acid (GalA) content, molecular weight and intrinsic viscosity meanwhile commercial low-methoxyl pectin (CLMP) as comparison. This study finds out a potential source of natural LMP which expands the application scope of sunflower heads. It is an efficient reuse of waste resources and provides a novel thought to explore the natural resources for food and pharmaceutical applications.