A fast 2D/3D resist dissolution algorithm is used to quantify line-edge roughness and determine its relation to resist material parameters, such as the polymerization length distribution, the end-to-end distance and the radius of gyration, along with the effects of acid-diffusion. The same relation between surface roughness and exposure dose known to hold experimentally is also shown to be valid for line-edge roughness. Increasing average polymerization length results in increased values of line-edge roughness, radius of gyration and end-to-end distance establishing an immediate relation between material properties and measured line-edge roughness (LER). The effects of the edge depth and length of measurement and of the free volume on LER vs. are also investigated.