Operando and precisely probing aqueous pH is fundamentally demanded, both in chemical and biological areas. Conventional pH probes, subjected to the larger size, are probably unfit for application in some extreme scenarios, such as a trace amount of samples. In this paper, we have further developed the pH sensor that leverages the microfiber Bragg grating with an ultra-compact size down to an order of magnitude of 10−14 m3. Using the electrostatic self-assembly layer-by-layer technique, the functional film consisting of sodium alginate, which harnesses a pH-dependent hygroscopicity, is immobilized on the fiber surface. Consequently, the alteration of aqueous pH could be quantitatively indicated by the wavelength shift of the grating resonance via the refractive index variation of the sensing film due to the water absorption or expulsion. The grating reflections involving fundamental mode and higher order mode exhibit the sensitivities of −72 pm/pH and −265 pm/pH, respectively. In addition, temperature compensation can be facilitated by the recording of the two reflections simultaneously. Furthermore, the modeling and simulation results predict the pivotal parameters of the configuration in sensitivity enhancement. The proposed proof-of-concept enriches the toolbox of pH sensor for catering to the need of detection in some extremely small spaces—for example, the living cells or the bio-tissues.