Using electrocatalysts is effective in solving the slow reaction kinetics of polysulfides in Li-S batteries, but designing stable electrocatalysts with an integrated adsorption-catalysis-desorption system is challenging. Here, we report a stable metal-semiconductor (Co-ZrO2) heterojunction electrocatalyst fabricated by assembling electron-coupled Co-ZrO2 nanodots into macroporous carbon nanofibers. The Co-ZrO2 contact causes interfacial electron enrichment and electron transfer from Co to ZrO2, which creates abundant Lewis-acid sites on Co that can adsorb polysulfides. Simultaneously, the enriched interfacial electrons can activate the S-S bond and boost the catalytic conversion of long-chain polysulfides, while the ZrO2 with Lewis-base sites facilitate the desorption of short-chain polysulfides from the electrocatalyst. Moreover, the nanodot heterojunctions show great chemical stability and high redox reaction kinetics of polysulfides. Li-S batteries show high discharge capacities of 954.5 mA h·g-1 at 0.5 C with a retention of 84.9% over 200 cycles, and 710.2 mA hg-1 at 1 C with a retention of 98.6% over 200 cycles. This study provides an effective strategy for developing active and durable electrocatalysts for Li-S batteries.