To establish the identity and quality of safflower petals used as herbal tea, four spiny and non-spiny cultivars (APRR3, TSF-1, NARI-NH-01, and NARI-06) were analyzed for various pharmacognostic characters, toxic metals (As, Pb, Hg, Cr, Cd by atomic absorption spectroscopy), pesticide residue (GC-ECD/PFPD), and flavonoid constituents, like quercetin, quercetin-3-O-rutinoside, and kaempferol, by high performance thin layer chromatography. Arsenic and lead were found to be absent in the decoction of all varieties. Although mercury and chromium were detected in standard acceptable levels, cadmium was exceeding the limit except in APRR3 (0.3 mg/kg). While none of the samples contained pesticide residue and saponins, presence of tannins (19–25%), bitterness principle (1257–2200 units/g), mucilaginous substances (0.93–2.83 mL/g), and volatile matter (4–16%) were observed and estimated in all varieties. Microscopic examination of NARI-06 and APRR3 petals explored similar features having slightly thick cylindrical style with dense spikes and corolla tube with five slightly thick ridges possessing ribbon like outgrowths. High performance thin layer chromatography analysis revealed APRR3 to possess higher amount of quercetin (116.6 ng/g), quercetin-3-O-rutinoside (189.7 ng/g), and kaempferol (185.07 ng/g). Thus, the spiny APRR3 safflower petals encompassing anti-oxidative flavonoids and complying heavy metals test, was identified as a safe variety for human consumption.