In this paper, graphene was used as the adsorbent for peptide enrichment, and followed by matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) analysis. To study the adsorptive property of graphene, peptide angiotensin II was chosen as the model target. The enrichment material was analyzed by MALDI-TOF MS directly without desorption step. As a result, graphene showed good adsorptive capacity for peptide. After enrichment, the peak intensity and the signal-to-noise ratio were obviously increased.