A new approach to the experimental investigation of heterogeneous crystallization on surfaces with molecularly defined structures is demonstrated. Crystallization and competitive dewetting processes of polyethylene on heterogeneous micropatterned surfaces were studied using molecular imprinting techniques for structured chemical modification of surfaces on micrometer scale in laterally defined areas. Examination of spherulitic textures by low-voltage SEM and AFM shows remarkable differences in spherulite sizes due to surface chemical influences. The results are discussed in terms of a diffusion limited aggregation process which causes the dendritic and spherulitic structures and which is influenced by the dewetting process.