Confocal laser scanning microscope (CLSM) has great advantage over a conventional microscope because it rejects the light that does not come from the focal plane, enabling one to perform optical slicing and construction of three-dimensional (3D) images. Further its high axial resolution, sharp image quality and associated quantitative image analysis provide vital structural information in the mesoscopic range for the full 3D realization of the microstructure. Because of this unique feature, CLSM is now finding wider applications in the study of variety of materials and processes such as phase separation in binary polymer mixtures, fracture toughness in alloys, in determining residual strains in fibre-reinforced metal composites, and in microvisualization of corrosion. This paper reviews some of these recent applications and also discusses our results on colloidal dispersions. CLSM has been used to characterize the amorphous structure in highly-charged colloidal systems which have undergone gas-solid transition. CLSM images show presence of large voids deep inside the disordered suspensions. Frame averaged images reveal that the structural disorder is amorphous. The reasons for voids coexisting with dense amorphous regions and their implications on colloidal interactions are discussed. The article also reviews the use of fluorescence-CLSM in the investigation of novel materials of technological importance such as template-directed colloidal crystals with preferred orientations and multilayered structures with different crystal plane symmetries. Direct measurement of the interfacial curvatures for a bicontinuous polymer blend system as well as real space measurement of structure in phase separating polymer mixtures are now possible using CLSM. This paper reviews some of these results highlighting the unique advantages of confocal microscopy for better understanding of the microstructure and mechanistic aspects of various important phenomena in a large variety of materials.