The concentration of nitric oxide (NO) in exhaled breath is linked to respiratory diseases, requiring precise detection. Traditional two-dimensional (2D) carbon-based materials used in chemiresistive gas sensors suffer from high detection limits due to a lack of functional sites, while metal oxide sensors are limited by poor selectivity and high operating temperatures, restricting their development. Recently, metal–organic frameworks (MOFs) have emerged as an effective material for NO monitoring due to their superior selectivity; however, their inherent insulating properties hinder practical use. In this study, we synthesized Ni, Co-MOF-74-Carbon Nanotube (CNT) heterostructured nanoflowers, leveraging their bimetallic active sites and large specific surface area to enhance NO adsorption. This composite material, integrated with breathable nanofibrous membranes through physical deposition, exhibits high selection to NO, achieving a linear response range of 30 to 1000 ppb at room temperature and a limit of detection (LOD) of 18.6 ppb. This sensor can accurately detect NO levels in the exhaled breath of both healthy and diseased individuals, confirming its potential for respiratory disease diagnosis. Additionally, we developed a portable device integrating the Ni, Co-MOF-74-CNT- polyacrylonitrile (PAN) membrane, a microcontroller unit (MCU), and a Bluetooth module for real-time NO detection. The systematic design and successful validation of this portable gas sensor pave the way for future home-based real-time monitoring of airway inflammation.