Diffusion-Weighted Imaging is a MRI technique that is able to distinguish between benign and malignant breast tumours via the Apparent Diffusion Coefficient (ADC). Nevertheless, this parameter provides very limited information regarding tissue microstructure. Here, is presented an approach to estimate the intracellular (Di) and extracellular (De) diffusion coefficients, and cell membrane permeability of tumour tissues which makes use of known ADC values, histological images and Monte-Carlo simulations of diffusion processes. Results show that distinct combinations of (Di, De, P) correlate with tumour type, and that a decreased De was observed in malignant tumours in agreement with known extracellular matrix changes.