Conversion　of　coal,　biomass,　and　organic　waste　to　combustible　gases　H2　and　CH4　in　supercritical　water　(SCW)　is　an　economically　and　environmentally　favored　technology.　Homogeneous　alkaline　catalysts　are　commonly　added　to　achieve　high　conversion　efficiency,　as　alkalis　are　believed　to　accelerate　the　gasification　of　aromatic　structures,　which　is　the　bottleneck　of　the　whole　gasification　process.　Nevertheless,　the　mechanism　of　how　alkali　metals　influence　the　reaction　of　aromatic　structures　is　still　not　acknowledged　clearly.　In　this　work,　different　pretreatments　of　the　high-alkali　metal　content　Zhundong　coal　are　taken　as　the　object　to　study　the　effect　of　naturally　present　and　artificial　additive　alkali　metals　on　the　microcrystalline　carbon　structure　and　their　reactivity　with　H2O　during　the　supercritical　water　gasification　(SCWG)　process.　XRD　analysis　was　applied　to　reveal　that　alkali　metals　inhibit　the　growth　of　graphite-like　structures　during　SCWG.　Subsequently,　the　separated　smaller　sized　aromatic　structures　are　indicated　by　calculating　the　Fukui　function　values　of　peripheral　carbon　atoms　to　exhibit　higher　reactivity　with　H2O　and　the　free　radicals　in　SCW.　Finally,　the　existence　of　alkali　metals　is　proven　to　promote　the　strong　chemisorption　of　H2O　on　carbon　structures,　which　is　the　premise　of　carbon　abstraction　of　the　aromatics,　via　thermogravimetric　analysis.　The　influence　of　different　reactors　and　SCW　is　also　involved　in　the　discussion.　This　work　is　prospective　for　optimal　utilization　of　the　homogeneous　catalysts　and　developing　innovative　catalysts.　©