The invention discloses 304 metastable-state austenitic stainless steel and a preparation process thereof. The 304 metastable-state austenitic stainless steel has the following steel components in percentage by mass: C less than 0.02%, 1.0-1.5% of Si, 1.0-2.0% of Mn, 19-21% of Cr, 9-12% of Ni, 1.5-2.5% of Cu, 0.03-0.05% of Nb, N less than 0.035%, and the balance of Fe and inevitable impurities; the fraction of ferritic phases is 50-80%; the balance comprises austenitic phases; the Md30 value given by the formula (A) is -20-20 DEG C; and Md30=551-462(C+N)-9.2(Si)-8.1(Mn)-29(Ni+Cu)-13.7(Cr)-18.5(Mo)...(A). The preparation process comprises the procedures of (S1) molten steel casting, (S2) hot-rolled annealing and (S3) cold rolling. The 304 metastable-state austenitic stainless steel has thetechnical effects of difficult cracking or rupture, excellent stretching performance and convenience for molding.