A novel fiber-optic ammonia Mach-Zehnder interferometer (MZI) with an asymmetric-sensing structure was developed and experimentally validated. The sensor was fabricated through successive fusion splicing of single-mode fiber (SMF), coreless fiber (NCF), SMF, thin-core fiber (TCF), and SMF, thereby forming an SMF-NCF-SMF-TCF-SMF interferometric structure. Experimental and simulation results demonstrated that the sensor exhibited a linear response within the refractive index range of 1.3320-1.3636. Using the layer-by-layer (LbL) self-assembly technique, ultrathin two-dimensional (2D) self-assembled tetrakis(4-carboxyphenyl) zinc porphyrin (SA-ZnTCPP) and zinc acetate (Zn(OAc)2) nanoporous films were deposited onto the fiber sensing region. The structural, morphological, and compositional properties of the nanomaterials and films were analyzed via Fourier-transform infrared (FT-IR) spectroscopy, ultraviolet-visible (UV-Vis) absorption spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). NH3 adsorption by the thin film modifies the sensor's effective refractive index, enabling gas detection. Experimental results revealed that the interference intensity of the monitoring peak increased proportionally with NH3 concentration. Within the 0-600 ppb range, the sensor demonstrated high sensitivity (7.12 dB/ppm) and linearity, achieving a detection limit of 2 ppm with response-recovery times of 40 s and 50 s, respectively. The sensor demonstrates notable advantages, including high sensitivity, excellent selectivity, straightforward design, and ultra-low detection limits, indicating strong potential for toxic NH3 monitoring in chemical engineering and industrial applications.