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Aim Methodology Results Conclusions Calcium hydroxide (CH) has been considered as a direct pulp capping materials (DPC) for the last decades despite having some limitations. Phosphorylate pullulan (PPL) incorporated with CH (CHPPL) is a novel biomaterial that was introduced as a promising DPC material. Thus, the aim of the study was to evaluate the inflammatory response and mineralized tissue formation (MTF) ability of PPL‐based CH formulations on rat molars after DPC.This study consisted of six groups: CH with 1% PPL (CHPPL‐1); 3% PPL (CHPPL‐3); 5% PPL (CHPPL‐5); Dycal and NEX MTA Cement (N‐MTA) as the positive control, and no capping materials (NC). One hundred twenty maxillary first molar cavities were prepared on Wistar rats. After capping, all the cavities were restored with 4‐META/MMA‐TBB resin and pulpal responses were evaluated at days 1, 7, and 28. Kruskal–Wallis followed by Mann–Whitney U‐test was performed with a significance level of 0.05. Immunohistochemical expression of IL‐6, Nestin, and DMP‐1 was observed.At day 1, CHPPL‐1, N‐MTA, and Dycal exhibited no to mild inflammation, whilst CHPPL‐3, CHPPL‐5, and NC showed mild to moderate inflammation, and the results were significantly different (p < .05). At day 7, mild to moderate inflammation was observed in CHPPL‐1, N‐MTA, and Dycal, whereas CHPPL‐3, CHPPL‐5, and NC exhibited moderate to severe inflammation. Significant differences were observed between CHPPL‐1 and N‐MTA with NC (p < .05), CHPPL‐1 and CHPPL‐3 with CHPPL‐5 and Dycal (p < .05), and CHPPL‐3 with N‐MTA (p < .05). A thin layer of mineralized tissue formation (MTF) was observed in all groups. At day 28, CHPPL‐1, Dycal, and N‐MTA showed no to mild inflammation, whilst CHPPL‐3, CHPPL‐5, and NC exhibited mild to severe inflammation, and statistically significant difference was detected (p < .05). CHPPL‐1, Dycal, and N‐MTA exhibited continuous MTF, whilst CHPPL‐3, CHPPL‐5, and NC had thicker and interrupted MTF. Significant differences were observed between CHPPL‐1, CHPPL‐3, and N‐MTA with NC group (p < .05). Variable expressions of IL‐6, Nestin, and DMP‐1 indicated differences in the materials' impact on odontoblast‐like cell formation and tissue mineralization.These findings suggest that CHPPL‐1 has the potential to minimize pulpal inflammation and promote MTF and had similar efficacy as MTA cement. [ABSTRACT FROM AUTHOR]