Imaging of surfaces and structures by near-field scanning optical microscopy (NSOM) has matured and is routinely used for studies ranging from biology to materials science. Of interest in this review paper is a versatility of modified or multi-functional NSOM (mf-NSOM) to enable high resolution imaging in several modes: (1) Concurrent fluorescence and Topographical Imaging (gases) (2) Microspectroscopy (gases) (3) Concurrent Scanning Electrochemical and Topographical Imaging (SECM) (liquids) (4) Concurrent Photoelectrochemical and Topographical Imaging (PEM) (liquids) The present study will summarize some of the recent advances in mf-NSOM work confirmed and supported by the results from several other imaging techniques of optical, fluorescence, electron and electrochemical microscopy. The studies are directed at providing local information on pitting precursor sites and vulnerable areas on metal and semiconductor surfaces, and at reactive sites on heterogeneous, catalytic substrates, especially on Al 2024 alloy and polycrystalline Ti. In addition, we will introduce some results related to the laser-induced nanometal (Ag) synthesis using mf-NSOM.