Anthropogenic emission of CH4 and CO2 contributes for most of global warming. Hence, simultaneous conversion of CH4 and CO2 into syngas (dry reforming of methane) can be a promising way to alleviate climate change. In this work, we developed a series of perovskite-type photocatalysts, based on LaFeO3 with various calcination temperatures to combine with a spark discharge reactor to form a hybrid plasma photocatalysis reactor. The hybrid reactor is applied for dry reforming of methane to investigate the syngas generation rate and to reveal possible interactions between plasma and photocatalyst. Results show that LFO600-packed bed has the best CH4 and CO2 conversions and syngas generation efficiency of 53.6%, 40.0% and 18.4 mol/kWh, respectively. The enhancement of syngas generation rate can be attributed to synergies between LFO and plasma. Furthermore, changing calcination temperature of photocatalyst also leads to variable characteristics of photocatalyst and hence plasma photocatalysis performance for syngas production.