Objectives: To evaluate the association between pretreatment MRI descriptors and breast cancer (BC) pathological complete response (pCR) to neoadjuvant chemotherapy (NAC). Materials \& Methods: Patients with BC treated by NAC with a breast MRI between 2016 and 2020 were included in this retrospective observational single-center study. MR studies were described using the standardized BI-RADS and breast edema score on T2-weighted MRI. Univariable and multivariable logistic regression analyses were performed to assess variables association with pCR according to residual cancer burden. Random forest classifiers were trained to predict pCR on a random split including 70% of the database and were validated on the remaining cases. Results: Among 129 BC, 59 (46%) achieved pCR after NAC (luminal (n=7/37, 19%), triple negative (TN) (n=30/55, 55%), HER2+ (n=22/37, 59%). Clinical and biological items associated with pCR were BC subtype (p<0.001), T stage 0/I/II (p=0.008), higher Ki67 (p=0.005) and higher tumor-infiltrating lymphocytes levels (p=0.016). Univariate analysis showed that the following MRI features, oval or round shape (p=0.047), unifocality (p=0.026), non-spiculated margins (p=0.018), no associated non-mass enhancement (NME) (p = 0.024) and a lower MRI size (p = 0.031) were significantly associated with pCR. Unifocality and non-spiculated margins remained independently associated with pCR at multivariable analysis. Adding significant MRI features to clinicobiological variables in random forest classifiers significantly increased sensitivity (0.67 versus 0.62), specificity (0.69 versus 0.67) and precision (0.71 versus 0.67) for pCR prediction. Conclusion: Non-spiculated margins and unifocality are independently associated with pCR and can increase models performance to predict BC response to NAC. Clinical Relevance Statement: A multimodal approach integrating pretreatment MRI features with clinicobiological predictors, including TILs, could be employed to develop machine learning models for identifying patients at risk of non-response. This may enable consideration of alternative therapeutic strategies to optimize treatment outcomes