Activating the defense response of plants by elicitors provides a promising method for biocontrol of pathogens. The homogeneous octaose (RiOc) which was depolymerized from the succinoglycan Riclin was investigated as a novel elicitor to activate the immune system of potato (Solanum tuberosum L.). After foliar spray, RiOc quickly induced accumulation of reactive oxygen species in potato leaves in a dose-dependent manner. Transcriptomic analysis revealed that 2712 out of 30,863 genes were differentially expressed at the early stage (24 h), while 367 of them were changed later (72 h). Results from the transcriptome and quantitative RT-PCR suggested that RiOc was probably perceived by the receptor LYK3 and it activated the MKK2/3/9/-MPK6/7 signaling cascade and promoted the salicylic acid-mediated defense response. Meanwhile, RiOc changed the metabolome profile of potato leaves over time as demonstrated by the H-1 NMR-based metabolomic analysis. Homeostasis of amino acids was affected at the early stage while the secondary metabolism was strengthened later. More importantly, RiOc significantly reduced the severity of potato leaf lesions caused by the late blight pathogen Phytophthora infestans. In conclusion, RiOc effectively improved the resistance of potato to P. infestans by eliciting the salicylic acid-mediated defense response. RiOc becomes a promising carbohydrate-based elicitor for biocontrol of plant pathogens.