This work mainly involves the study of effect of relative humidity on adsorption of formaldehyde on the activated carbons modified with organosilane solution. Modification of activated carbons was carried out by impregnating activated carbon with organosilane/methanol-containing solutions. The breakthrough curves of formaldehyde in the packed beds of original and modified activated carbons were measured, respectively, at relative humidity of 30%, 60%, and 80%. Temperature-programmed desorption (TPD) experiments were used to estimate the activation energy for desorption of formaldehyde from the activated carbon. Results showed that the relative humidity had strongly influence on breakthrough curves of formaldehyde in the packed beds. The higher the relative humidity of gas mixtures through the packed beds was, the smaller the breakthrough time of formaldehyde became. The use of organosilane compounds to modify surfaces of the activated carbon can enhance the interaction between formaldehyde and the surfaces, and as a result, the breakthrough times of formaldehyde in the packed beds of the modified activated carbon were longer than that in the packed bed of the unmodified activated carbon.