TLCP/nylon-66　molecular　composites　were　compounded　by　solution　blend.　Crystallization　and　miscibility　were　researched　by　DSC,　WAXD　and　FTIR.　DSC　results　showed　that　composites　melting　points　and　crystallization　temperature　were　reduced　due　to　additional　TLCP,　and　crystallization　rate　and　crystallization　degree　tended　to　decrease.　Composites　demonstrated　supramolecular　liquid-crystalline　behavior　in　50%　(mass　fraction)　TLCP　ratio.　WAXD　results　showed　that　distance　between　crystalline　surfaces　increased　while　increasing　TLCP　concentrations,　so　it　can　be　certain　that　TLCP　had　taken　part　in　nylon-66　crystallization　process.　According　to　DSC　and　WAXD　results,　TLCP　apparently　restrain　crystallization　of　nylon-66.　FTIR　approved　that　there　was　intermolecular　hydrogen-bonding　between　molecules　of　TLCP　and　nylon66,　and　intensity　of　intermolecular　hydrogen-bonding　increased　with　increasing　TLCP　concentrations.