Melatonin is a pleiotropic, nontoxic, regulatory biomolecule with various functions in abiotic stress tolerance. It reverses the adverse effect of heat stress on photosynthesis in plants and helps with sulfur (S) assimilation. Our research objective aimed to find the influence of melatonin, along with excess sulfur (2 mM SO42−), in reversing heat stress’s impacts on the photosynthetic ability of the mustard (Brassica juncea L.) cultivar SS2, a cultivar with low ATP-sulfurylase activity and a low sulfate transport index (STI). Further, we aimed to substantiate that the effect was a result of ethylene modulation. Melatonin in the presence of excess-S (S) increased S-assimilation and the STI by increasing the ATP-sulfurylase (ATP-S) and serine acetyltransferase (SAT) activity of SS2, and it enhanced the content of cysteine (Cys) and methionine (Met). Under heat stress, melatonin increased S-assimilation and diverted Cys towards the synthesis of more reduced glutathione (GSH), utilizing excess-S at the expense of less methionine and ethylene and resulting in plants’ reduced sensitivity to stress ethylene. The treatment with melatonin plus excess-S increased antioxidant enzyme activity, photosynthetic-S use efficiency (p-SUE), Rubisco activity, photosynthesis, and growth under heat stress. Further, plants receiving melatonin and excess-S in the presence of norbornadiene (NBD; an ethylene action inhibitor) under heat stress showed an inhibited STI and lower photosynthesis and growth. This suggested that ethylene was involved in the melatonin-mediated heat stress reversal effects on photosynthesis in plants. The interaction mechanism between melatonin and ethylene is still elusive. This study provides avenues to explore the melatonin–ethylene-S interaction for heat stress tolerance in plants.