In this study, one-year-old seedlings of Paeonia ostii ‘Fengdan’ were used as materials. The method of spraying exogenous salicylic acid (SA), calcium chloride (CaCl₂) and abscisic acid (ABA) was used. The effects of different concentrations of SA, CaCl₂ and ABA on the heat tolerance of peony seedlings under high temperature stress were studied. The optimum concentration and mechanism of SA-, CaCl₂- and ABA-induced heat tolerance of peony seedlings under high temperature stress were discussed. The results showed that 100 μmol/L SA, 40 mmol/L CaCl₂ and 40 mg/L ABA had the best induction effect on the heat tolerance of peony. The effects of three exogenous substances on the heat resistance of peony seedlings were ranked as SA > CaCl₂ > ABA. The three exogenous substances mainly alleviated high temperature damage by alleviating the degradation of chlorophyll (Chl), relative electrical conductivity (Rec) content, increasing superoxide dismutase (SOD) activity, soluble proteins (SPs), free proline (Pro) and soluble sugars (SSs) content, and reducing SSs content under high temperature stress. The five indices had the most significant effect on the three exogenous substances in improving the heat resistance of peony seedlings. These could be used as an index to identify the heat resistance.