Bamboo is one of the most important non-wood raw materials for the pulp and paper industry in Asia and particularly in China. However, its high silicon content can cause challenges in the pulping and alkali recovery systems. Further understanding of the distribution, morphology, and composition of silicon in bamboo culm will be beneficial in solving these challenges. In this study, modern analytical tools such as scanning electron microscopy (SEM) and scanning electron microscopy equipped with an energy dispersive X-ray (SEM-EDX) were used to characterize the distribution, morphology, and composition of silicon in the bamboo culm. The results showed that silicon is mainly distributed in the outer skin and inner skin. The silicon deposits exist in a number of shapes, and sinuate is the most common one. Their sizes range from about 0.15 μm to 0.9 μm in the cell wall and between 0.3 μm to 1.5 μm in the cell lumen. Localized silicon deposits are present in the forms of its oxide, silica, monatomic silicon, and/or organosilicon. Based on the above results, two potential techniques are recommended for pulp mills to minimize silicon-related challenges.