Fractional exhaled nitric oxide (FeNO) can be used to describe inflammatory processes in the respiratory tract. Directly detecting ppb-level nitric oxide (NO) with chemiresistive sensors at room temperature faces the challenges of simultaneously obtaining high sensitivity and high stability for sensors. We aimed to improve the stability and sensitivity of NO sensors. We assembled sheet-like porphyrin-based MOF DLS-2D-Co-TCPP(Fe) with 5-aminonaphthalene-1-sulfonic acid-rGO (ANS-rGO) nanosheets through coordination interactions. In this way, we offered a room-temperature NO-sensing hybrid, DLS-2D-Co-TCPP(Fe)/ANS-rGO, with a sheet-on-sheet (SOS) architectural heterojunction. The DLS-2D-Co-TCPP(Fe)/ANS-rGO-based sensor demonstrated superior NO-sensing performance, including high sensitivity (R_a/R_g = 1.33, 250 ppb), reliable repeatability, high selectivity, and fast response/recovery (150 s/185 s, 1 ppm) at a sensing concentration from 100 ppb to 10 ppm at room temperature. The obtained sensor showed high stability, retaining >85% of its initial response after 60 days. Designing NO-responsive Fe-N₄ active units containing MOF nanosheets, along with constructing a heterojunction with an SOS architecture to facilitate carrier migration, collaboratively dominated the superior performance of synthesized NO sensors. This work provides a strategy for designing SOS architectural heterojunctions to obtain high-performance MOF-based gas-sensing materials.