Abstract Background The potential role of cardiac computed tomography (CT) has increasingly been demonstrated for the assessment of diffuse myocardial fibrosis through the quantification of extracellular volume (ECV). Photon-counting detector (PCD)-CT technology may deliver more accurate ECV quantification compared to energy-integrating detector CT. We evaluated the impact of reconstruction settings on the accuracy of ECV quantification using PCD-CT, with magnetic resonance imaging (MRI)-based ECV as reference. Methods In this post hoc analysis, 27 patients (aged 53.1 ± 17.2 years (mean ± standard deviation); 14 women) underwent same-day cardiac PCD-CT and MRI. Late iodine CT scans were reconstructed with different quantum iterative reconstruction levels (QIR 1−4), slice thicknesses (0.4−8 mm), and virtual monoenergetic imaging levels (VMI, 40−90 keV); ECV was quantified for each reconstruction setting. Repeated measures ANOVA and t-test for pairwise comparisons, Bland–Altman plots, and Lin’s concordance correlation coefficient (CCC) were used. Results ECV values did not differ significantly among QIR levels (p = 1.000). A significant difference was observed throughout different slice thicknesses, with 0.4 mm yielding the highest agreement with MRI-based ECV (CCC = 0.944); 45-keV VMI reconstructions showed the lowest mean bias (0.6, 95% confidence interval 0.1–1.4) compared to MRI. Using the most optimal reconstruction settings (QIR4. slice thickness 0.4 mm, VMI 45 keV), a 63% reduction in mean bias and a 6% increase in concordance with MRI-based ECV were achieved compared to standard settings (QIR3, slice thickness 1.5 mm; VMI 65 keV). Conclusions The selection of appropriate reconstruction parameters improved the agreement between PCD-CT and MRI-based ECV. Relevance statement Tailoring PCD-CT reconstruction parameters optimizes ECV quantification compared to MRI, potentially improving its clinical utility. Key points • CT is increasingly promising for myocardial tissue characterization, assessing focal and diffuse fibrosis via late iodine enhancement and ECV quantification, respectively. • PCD-CT offers superior performance over conventional CT, potentially improving ECV quantification and its agreement with MRI-based ECV. • Tailoring PCD-CT reconstruction parameters optimizes ECV quantification compared to MRI, potentially improving its clinical utility. Graphical Abstract