The study of the physicochemical process of volatile organic compound (VOC) adsorption on porous materials is significant for design and screening of adsorbent materials and treatment of VOCs. Traditional measurement methods for studying the adsorption process require lots of adsorbates and adsorbents and are time-consuming. We proposed a facile strategy to study the adsorption process of trace gaseous aldehydes on layered double hydroxide (LDH) using surface-enhanced Raman spectroscopy (SERS). We prepared a composite of Ag nanocubes@hollow Co-Ni LDH (AgNCs@Co-Ni LDH) with a strong adsorption capability and high SERS sensitivity. The adsorption properties of LDH for benzaldehyde in terms of general kinetics and isotherms were investigated. The kinetic adsorption process could be fitted better by the pseudo-first-order kinetics with a higher correlation coefficient than by the pseudo-second-order model, and the adsorption rate of 0.0308 min-1 was obtained from the fitting curve. The isotherm adsorption fits the Langmuir isotherm model, and its adsorption constant is 6.25 × 106 L/mol. Taking advantage of the excellent adsorptive performance and SERS activity, the AgNCs@Co-Ni LDH composite can be used as an effective SERS probe to detect gaseous aldehydes, and it shows a linear dynamic range (5-100 ppb) with a limit of detection reaching 1.83 ppb for benzaldehyde, better than that achieved by previous studies. Therefore, this work has not only established a new measurement method for probing the adsorption process with extremely low consumption of both adsorbates and adsorbents, but also may lay the groundwork for the construction of rapid and ultra-sensitive SERS sensors for probing VOCs in the future.