A pulsed laser engineering approach is developed to prepare novel functional graphene paper with graphitic nanospheres homogeneously decorated on the surface and the superior performance of engineered paper is revealed in matrix-free mass spectrometry (MS) detection and imaging. We demonstrate that the stability of graphene paper under intense irradiation can be dramatically increased through a designed laser engineering process by forming densely packed graphitic nanospheres on the paper surface. Moreover, the surface hydrophobicity is enhanced and electric conductivity is improved. The engineered graphene paper can image the invisible micro-patterns of trace amount molecules and increases the detection limit towards diverse molecules by over two orders of magnitude compared to the pristine graphene paper and commercial products in MS analysis.