This paper presents an innovative mechano-chemical process to extract high purity bamboo short micron fibers (BMFs) through a face-centered central composite design; the processing parameters were optimized by a response surface method. After optimization % yield of BMFs as high as 45 was achieved. Analysis of variance and parametric analysis have been carried out to determine the most influencing parameters on the % yield of BMFs. Furthermore, the morphological investigation of the high yield BMFs under scanning electron microscope (SEM) discloses well-separated fibers having reduced cellulose surface peeling. Grafting benzoyl function groups on the surfaces of BMFs was tried to enhance their hydrophobicity. The produced benzoyl function group grafted BMFs exhibit a smoother surface with reduced scalloped components. The surface modification of the BMFs was confirmed by the Fourier transform infrared spectrometry (FTIR) studies. Moreover, a three-step thermal degradation behavior was observed for the benzoylated BMFs, which also endorses their surface modification. As expected, liquid retention value for the benzoylated BMFs was significantly reduced, confirming enrichment of hydrophobicity. Also, the benzoylated BMFs are found to have improved thermal stability. This detailed investigation opens up the scope of using such juvenile bamboo short micron fibers in various industries.