The　searching　for　new　nonvolatile　memories　with　the　ability　of　working　in　harsh　environments　such　as　high　temperature　or　humidity　will　be　significant　for　industrial　automation.　Herein,　a　thermochromic　polyoxometalate-based　metal-organic　framework　(POMOF)　constructed　from　Keggin-type　polyoxometalates　and　metalloviologen　has　been　fabricated　as　a　nonvolatile　memory　device,　which　can　exhibit　stable　nonvolatile　memory　behavior　both　at　room　and　high　temperature　(150　°C)　with　stable　cycle　performance.　Furthermore,　its　extreme　working　temperature　can　be　monitored　by　color　change　from　yellow　to　black,　which　stems　from　the　reversible　thermochromism　of　the　POMOF.　Importantly,　the　crystal　structures　at　room　and　high　temperature　(150　°C)　have　been　determined,　which　illustrates　that　the　Keggin-type　POM　(α-GeW12O40)4-　anions　are　anchored　in　the　metalloviologen　cationic　[Co2(bpdo)4(H2O)6]n4n+　cavities　through　numerous　C-H···OPOM　hydrogen　bonds.　The　high　temperature　could　not　destroy　its　framework　but　remove　its　three　lattice　water　molecules;　in　addition,　more　condensed　structures　with　shorter　Ge/W/Co-O　lengths,　stronger　hydrogen　bonds,　and　more　distorted　terminal　bpdo　ligands　can　be　observed.　Consequently,　better　cycling　stability　with　a　more　uniform　high-resistance　state/low-resistance　state　can　be　achieved.　Finally,　the　charge　transport　mechanism　in　this　POMOF-based　device　during　the　resistive　switching　process　has　been　discussed.　In　all,　the　combination　of　electron-poor　metalloviologen　with　electron　reservoir　POM　can　give　rise　to　the　enhanced　nonvolatile　memory　and　better　thermal　stability　accompanied　with　observable　chromism.　©　2021　American　Chemical　Society.