We report on layer-by-layer (LbL) deposition of tannic acid (TA)/neutral polymers and their stability in the pH scale. The neutral polymers used for hydrogen-bonding with TA were poly(N-vinylcaprolactam) (PVCL), poly(N-vinylpyrrolidone) (PVPON), poly(ethylene oxide) (PEO) or poly(N-isopropyl acrylamide) (PNIPAM). LbL film deposition and pH-stability were followed by phase-modulated ellipsometry and in situ Fourier transform infrared spectroscopy in attenuated total reflection mode (ATR-FTIR). Hydrogen-bonded films of TA with PVCL, PVPON, PEO, and PNIPAM were constructed at pH 2 and did not dissolve until a critical dissolution pH of 9.5, 9, 8.5 and 8 (measured in 0.01 M buffer solutions) for PVCL/TA, PVPON/TA, PEO/TA, and PNIPAM/TA, respectively. Incorporation of a polyacid with a low pKa, such as poly(aspartic acid) (PLAA), as the third polymer component into these films results in TA/PVCL/PLAA hybrid films, whose pH destruction profile can be tuned by varying film architecture, i.e. by depositing alternating or stacked PVCL/TA and PVCL/PLAA sublayers. High pH-stability of hydrogen-bonded TA films, as well as the capability of tuning the critical dissolution pH close to physiological pH values makes such multilayer systems promising candidates for biomedical applications.