How to effectively reduce anthropogenic greenhouse gases emission to alleviate global warming has been a public concern since 20th century. Hence, development of effective CO2 and CH4 reduction technique is a common objective worldwide. Simultaneous conversion of CO2 and CH4 into syngas can be a candidate to achieve the objective. Among several conversion techniques, plasma and photocatalysis are two promising techniques possessing good potentials. In this work, a spark discharge reactor and a series of perovskite-type photocatalysts are developed and combined to form hybrid plasma photocatalysis systems to evaluate the effectiveness for converting CO2 and CH4 to form syngas. Experimental results indicate that the spark discharge reactor packed with LFO600 photocatalyst increases the syngas generation rate from 13.0 to 18.5 mol per kilowatt-hour, corresponding to 42% of enhancement. Furthermore, characterizations of photocatalysts reveal that plasma can promote the surface structure of photocatalyst to increase the lifetime of electron-hole pairs which possibly leads to higher syngas generation rate. Additionally, the hybrid plasma photocatalysis system developed has been demonstrated with good potential to improve plasma and photocatalysis performances.