We report on enzymatically degradable nanothin coatings obtained by layer-by-layer (LbL) assembly of silk fibroin with poly(N-vinylcaprolactam) (PVCL) via hydrogen bonding and hydrophobic interactions. We found that both silk β-sheet content, controlled through dipping and spin-assisted LbL, and PVCL molecular weight regulate film thickness, microstructure, pH-stability, and biodegradability with a nanoscale precision. Thickness of (silk/PVCL) films increased with increase in PVCL molecular weight and decrease in deposition pH. The impact of assembly pH on film growth was more dramatic for dipped films. These systems show a significant rise in thickness with increase in PVCL molecular weight at pH < 5 but become independent on polymer chain length at pH ≥ 5. We also found that spin-assisted films exhibited a greater stability at elevated pH and against enzymatic degradation as compared to their dipped counterparts. For both film types, the pH and enzymatic stability was improved with increasing PVCL length and β-sheet content, indicating enhanced hydrophobic and hydrogen-bonded interactions between PVCL and silk. Finally, we fabricated spherical and cubical (silk/PVCL) LbL capsules of regulated permeability and enzymatic degradation. Our approach gives a unique opportunity to tune thickness, morphology, structure, and biodegradability rate of silk films and capsules by varying silk secondary structure and PVCL length. Accounting for all-aqueous fabrication and the biocompatibility of both polymers these biodegradable materials provide novel platforms for delivery systems and medical devices.