This present study demonstrated the preparation of a highly crystalline anatase (ana) form of titanium oxide (TiO) doped silk nanocrystal (SNC) nanohybrid (ana-TCS) of diameter (7.5 ± 1.4 nm) by the sol-gel method using titanium (IV) butoxide as the hydrolysis material. This prepared nanohybrid with surface hydroxyl groups acted as a co-initiator for the synthesis of poly(L-lactic acid) (PLLA)-g-ana-TSC nanocomposite with grafted PLLA chains via the in situ polymerization technique, using tin-octoate as a catalyst. The fabricated nanocomposite had a high number average molecular weight of 83 kDa with good processibility. This prepared nanocomposite was hydrophobic in nature, with a contact angle of 105°, which was further enhanced to 122 ± 1° when processed via electrospinning technique into a non-woven fabric. The prepared nanocomposite could degrade up to 43% methylene blue dye in 15 days. This nanocomposite showed no significant molecular weight reduction after 1 h of aqeous treatment, which could be attributed to its hydrophobic nature, inhibiting its degradation. However, 50% degradation was observed for the nanocomoposite whereas, PLLA demonstrated 25% degradation in 15 days, after its end-of-life. Thus, this study revealed that the in situ synthesized PLA-ana-TCS nanocomposite could be targeted for use as a hydrophobic, self-cleaning, dye-degradable fabric.