In silicon photonic waveguides, the on-chip integration of high-performance nanomaterials is considerably important to enable the waveguide sensing function. Herein, the in situ self-assembly of the low refractive index (RI) metal-organic framework nanomaterial ZIF-8 with a large surface area and high porosity on the surface of a designated SiO2 waveguide for evanescent wave sensing is demonstrated. The surface morphology and transmission loss of the nano-functionalized waveguide are investigated. The specific design and fabrication of asymmetric Mach-Zehnder interferometers (AMZIs) are performed based on the optical properties of ZIF-8. Such efforts in waveguide engineering result in an output interfering spectrum of nano-functionalized AMZI with an ultra-high extinction ratio (28.6 dB), low insertion loss (∼13 dB) and suitable free spectral range (∼30 nm). More significantly, the outstanding sensing features of ZIF-8 are successfully realized on the SiO2 waveguide chip. The results of ethanol detection show that the AMZI sensor has a large detection range (0 to 1000 ppm), high sensitivity (19 pm ppm-1 from 0 to 50 ppm or 41 pm ppm-1 from 600 to 1000 ppm) and low detection limit (1.6 ppm or 740 ppb). This combination of nanotechnology and optical waveguide technology is promising to push forward lab-on-waveguide technology for volatile organic compound (VOC) detection.