Selective synthesis of higher oxygenates from syngas is an important but challenging research target, and the present methods for converting syngas into oxygenates suffer from low selectivity and high energy consumption in multiple processes. Herein, we report a tandem catalyst composed of carbon-supported CoMn and Rh-metalated 3v-PPh3-based porous organic polymers (POPs), which can convert syngas to oxygenates with a selectivity of up to 62.7% and where the percentages of C2+ and C6+ oxygenates exceed 96.6 and 70.7%, respectively. The CoMn/modified activated carbon (MAC) works as a Fischer–Tropsch synthesis (FTS) catalyst to produce paraffins, olefins, and alcohols, and the Rh–P active site embedded on Rh/3v-PPh3@POPs serves as a heterogeneous hydroformylation catalyst to convert the obtained olefins into aldehydes. The present work puts forward an alternative strategy for the design of relay catalysts for the direct synthesis of higher oxygenates.