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Liquid sulfur undergoes a polymerization transition from S8 rings to a mixture of S8 rings and polymeric chains at Tp,= 159°C. Recently, we have found that such a transition can be induced below Tp through laser illumination and that there are three photo-excited structural stages, which are controlled by the laser intensity; (1) an intermediate product between a S8 ring and a polymer, produced by weak laser illumination, (2) a polymer, produced by medium laser illumination, and (3) ordered macromolecules, produced by strong laser illumination. In this paper, we report the details of these photo-structural changes and discuss the origin of these changes based on the electronic nature of a sulfuric chain which posses lone-pair electrons. [ABSTRACT FROM AUTHOR]