The　recovery　of　spent　hydrogenation　catalysts　occupies　advantages　in　both　alleviating　environmental　burden　and　resource　shortage.　Whereas,　the　development　of　conventional　hydrometallurgical　recovery　of　molybdenum　(Mo)　and　nickel　(Ni)　from　spent　MoNi/Al2O3　catalysts　has　been　limited　by　the　numerous　processes　and　the　accompanying　generation　of　waste　liquids　and　residues.　Herein,　A　new　recycling　route　for　the　preparation　of　spent　hydrogenation　catalysts　with　low　thermal　expansion　coefficients　(CTE)　was　proposed,　which　has　the　advantages　of　short　process,　green　environment　and　high　value　utilization.　The　Li2O-Al2O3-SiO2-B2O3　(LASB)　parent　glass　containing　Mo　and　Ni　were　obtained　by　melting　with　different　contents　of　the　spent　catalysts.　The　thermal　expansion　coefficient　of　the　glass　was　minimized　to　6.08　x　10-6/degrees　C　at　an　addition　of　25　wt%　of　the　spent　catalysts.　Moreover,　according　to　the　crystallization　peak　in　DTA　curve,　glass-ceramics　were　prepared　by　onestep　crystallization　heat　treatment　at　different　crystallization　temperatures.　The　main　crystalline　phase　of　the　glass-ceramic　precipitated　by　heating　at　685　degrees　C　is　beta-quartz　(Li2Al2Si3O10),　which　gives　the　glass-ceramics　the　lowest　coefficient　of　thermal　expansion　(0.96　x　10-6/degrees　C)　of　glass-ceramic　as　well　as　the　maximum　density　(2.45　g/cm3)　and　Vickers　hardness　(705.8　Hv).　Furthermore,　the　activation　energy　(354.65　+/-　17.42)　kJ/mol)　and　Avrami　index　(5.39)　associated　with　crystallization　were　extracted　from　the　fitting　of　different　theoretical　model,　indicating　the　three-dimensional　crystallization　of　the　LASB　glass-ceramics.　This　technology　provides　a　waste-tomaterial　strategy　for　hazardous　waste　and　a　clean　production　route　for　the　preparation　of　the　functional　glassceramics.