Formaldehyde emitted from household products is classified as a hazardous substance that can adversely affect human health. Recently, various studies related to adsorption materials for reducing formaldehyde have been widely reported. In this study, mesoporous and mesoporous hollow silicas with amine functional groups introduced were utilized as adsorption materials for formaldehyde. Formaldehyde adsorption characteristics of mesoporous and mesoporous hollow silicas having well-developed pores were compared based on their synthesis methods—with or without a calcination process. Mesoporous hollow silica synthesized through a non-calcination process had the best formaldehyde adsorption characteristics, followed by mesoporous hollow silica synthesized through a calcination process and mesoporous silica. This is because a hollow structure has better adsorption properties than mesoporous silica due to large internal pores. The specific surface area of mesoporous hollow silica synthesized without a calcination process was also higher than that synthesized with a calcination process, leading to a better adsorption performance. This research suggests a facile synthetic method of mesoporous hollow silica and confirms its noticeable potential as a support for the adsorption of harmful gases.