A fluorescence spectroscopic assay using Newton black film (NBF) for sensitive and selective detection of gaseous formaldehyde at room temperature is reported. The method relies on the Hantzsch reaction of formaldehyde with ammonium citrate and acetylacetone, plus a combination of the large surface area-to-volume ratio (5 × 10 m) and efficient uptake of gas by the nanometer-thick aqueous core of NBF. The assay has a limit of detection (LOD) of 4 ppb, a linear signal-to-concentration correlation up to 300 ppb of HCHO gas in the air, and a nonlinear monotonic increasing correlation in the range of 300 ppb to 1.2 ppm. It is unaffected by relevant analytes such as acetaldehyde, benzaldehyde, acetone, and propionaldehyde. We also demonstrate the sensing of formaldehyde outgassing from a plywood sample using this method and the results agree with the factory specifications.