Relations between phosphate and arsenate are important but inconsistent to influence arsenic (As) phytotoxicity depending on many plant and soil factors. Present research aimed to investigate the phosphate and arsenate interactions in sunflower (Helianthus annuus L.) grown in alkaline calcareous soil for 18 weeks under natural environmental conditions at three arsenate [0 (As), 40 (As), and 80 (As) mg As kg soil as sodium arsenate] and three phosphate [0 (P), 100 (P), and 200 (P) mg PO kg soil as diammonium phosphate] levels. The plants were grown in pots according to completely randomized design with five replications. Ionic and physiological parameters were measured at 40 days after treatment completion. Arsenic contamination with As and As increased root and shoot As concentration with relatively higher concentration in roots, malondialdehyde (MDA), superoxide dismutase (SOD), catalase (CAT), and peroxidase (POD) while decreased plant P, chlorophyll, protein, and glutathione (GSH), and consequently plant growth, yield, and yield attributes. Addition of P and P under As stress reduced As transfer from soil to roots to shoots, MDA concentration, SOD, CAT, and POD activities while increased GSH, leaf protein, chlorophyll, and growth characteristics as well as achene yield compared to As-treated plants without additional P. In conclusion, P-induced inhibition of As transfer from soil to roots to shoots and reduction in MDA concentration accompanied with an increase in the synthesis of protein, chlorophyll, and GSH could be the main mechanisms responsible for lowered As toxicity in sunflower, leading to mitigation of potential risks of As contamination to food chain and human health.