Mass　spectrometry　imaging　(MSI)　has　provided　a　new　perspective　on　acquiring　spatial　information　of　multiple　molecules　in　various　samples.　Among　the　different　ionization　methods,　matrix-assisted　laser　desorption/ionization　(MALDI)　has　been　widely　utilized　for　detecting　macromolecules,　with　difficulty　for　small　molecules　(m/z　＜　700 Da)　due　to　the　matrix　interference　or　ionization　suppression.　In　the　past　two　decades,　surface-assisted　laser　desorption/ionization　mass　spectrometry　(SALDI-MS)　gives　rise　to　lots　of　attention　on　account　of　its　unique　performances,　especially　in　untargeted　analysis　of　small　molecules.　Selecting　an　appropriate　substrate　is　a　precondition　for　SALDI-MS　and　offers　the　possibility　for　SALDI-MS　imaging　(SALDI-MSI).　In　the　last　5 years,　different　kinds　of　nanomaterials　have　been　widely　explored　as　substrates　including　metal/metal　oxide-based,　carbon-based,　silicon-based,　metal–organic　frameworks-based,　covalent　organic　frameworks-based　substrates,　with　growing　interests　on　composite　materials　and　nanomaterials　with　homogeneous　film　structure.　This　review　highlights　recent　advances　of　various　nanomaterials　as　SALDI　substrates,　and　their　emerging　imaging　applications　in　botanic,　forensic,　metabolic　and　pathological　fields.　Finally,　the　merits　and　limitations　of　SALDI-MS　are　sketched　out　and　some　recommendations　of　this　technique　and　its　imaging　are　proposed.　©　2022,　The　Nonferrous　Metals　Society　of　China.