Simplifications of systems are important for understanding their universal and/or intrinsic properties. Topology is one of the key concepts of such procedures, which focuses simply on the connectivity of the system to clarify the essential aspects of the geometric structures. To date, this concept has been extended to the field of physics, especially to the condensed matter physics and materials science. For example, topological defects have been observed in various materials, such as liquid crystals, superconductors, and electron gas systems in semiconductors. More recently, photoexcitations to some specific materials (mainly semiconductor nanostructures) have also revealed formation of topological defects. On the other hand, optical field itself includes a topological character, which has been well known as "optical or polarization vortex", "twisted light", and "helical or Laguerre-Gauss light" beams. These topological light beams exhibit spiral (spatial) variations of the phase (polarization) producing phase (polarization) singularities on the wavefront, which can be regarded as topological defects (screw dislocations). Therefore, we have possibilities to evaluate the topological aspects of material system on the interactions with topological light beams. However, the question arises: does it make any sense to apply the topological concept to the laser spectroscopy? The purpose of this chapter is to answer the question by introducing our recent research on this topic. Experimental results will be presented and discussed in terms of topological order of electrons. The chapter begins with the basics of topological light beams together with their important properties for laser spectroscopy (Sect. 3.1). Both the historical background and the overview of applications will also be introduced. In Sects. 3.2 and 3.3, we present several techniques for generating and evaluating the topological light beams, which are useful and needed in the experimental sections. We also discuss their advantages and drawbacks. In Sects. 3.4 and 3.5, we present our experimental results on