The rotational spectrum of the 1 : 1 benzaldehyde-formaldehyde complex has been investigated by pulsed jet Fourier transform microwave spectroscopy combined with ab initio calculations. The two most stable isomers were observed, with the relative abundance ratio NI/NII≈ 3/1 estimated with intensity measurements. Both observed isomers are stabilized by one dominating O[double bond, length as m-dash]CO tetrel bond (n →π* interaction) and one secondary C-HO hydrogen bond. Natural bond orbital analysis and electron localization function analysis were applied to characterize the nature of the noncovalent interactions in the target complex.