We have site-directedly linked a green fluorescent protein (GFP) variant and a β-cyclodextrin (β-CD) with a simple method to develop a basic complex for sophisticated supramolecules. We have confirmed β-CD grafting on GFP with several methods including matrix-assisted laser desorption/ionization linear time-of-flight mass spectrometry (MALDI-TOF MS) without protease digestion and characterized the complex as well. In consideration of the resulting properties, the product we plainly and efficiently obtained could have applications related to sensing devices and drug delivery systems.