The present invention relates to near-field scanning optical microscopy (NSOM) and near-field/far-field scanning microscopy methods, systems and devices that permit the imaging of biological samples, including biological samples or structures that are smaller than the wavelength of light. In one embodiment, the present invention permits the production of multi-spectral, polarimetric, near-field microscopy systems that can achieve a spatial resolution of less than 100 nanometers. In another embodiment, the present invention permits the production of a multifunctional, multi-spectral, polarimetric, near-field/far-field microscopy that can achieve enhanced sub-surface and in-depth imaging of biological samples. In still another embodiment, the present invention relates to the use of polar molecules as new optical contrast agents for imaging applications (e.g., cancer detection).