•A catalyst with isolated cobalt in siliceous zeolite was prepared •This catalyst catalyzed the EDH at thermodynamically limited conversion levels •Superior productivity of ethylene was achieved •The catalyst was coking resistant with constant performances over a long period Catalytic dehydrogenation of ethane (EDH) is promising for the utilization of shale gas to produce ethylene, but the current processes mostly exhibit space-time productivity of ethylene lower than 1.5 KgC2H4 Kgcat−1 h−1 because of the insufficient catalyst activity in the non-oxidative route. We reported a catalyst with isolated cobalt in siliceous zeolite derived from a mechanically assisted spontaneous dispersion. This material can operate as a non-oxidative EDH catalyst at thermodynamically limited conversion levels under rapid gas feeding, resulting in ethylene productivity at 13.4 KgC2H4 Kgcat−1 h−1. This result is superior to that of the previous non-noble metal catalysts and even outperforms the precious PtSn/Al2O3 catalyst. The isolated cobalt sites are preserved upon calcination at high temperatures and during EDH operation under harsh conditions, resulting in superior durability in a long reaction period with negligible coke formation. Catalytic dehydrogenation of ethane (EDH) is promising for the utilization of shale gas to produce ethylene, but the current processes mostly exhibit space-time productivity of ethylene lower than 1.5 KgC2H4 Kgcat−1 h−1 because of the insufficient catalyst activity in the non-oxidative route. We reported a catalyst with isolated cobalt in siliceous zeolite derived from a mechanically assisted spontaneous dispersion. This material can operate as a non-oxidative EDH catalyst at thermodynamically limited conversion levels under rapid gas feeding, resulting in ethylene productivity at 13.4 KgC2H4 Kgcat−1 h−1. This result is superior to that of the previous non-noble metal catalysts and even outperforms the precious PtSn/Al2O3 catalyst. The isolated cobalt sites are preserved upon calcination at high temperatures and during EDH operation under harsh conditions, resulting in superior durability in a long reaction period with negligible coke formation.