Per- and polyfluoroalkyl substances (PFASs) can penetrate the placental barrier and reach embryos through cord blood, probably causing adverse birth outcomes. Therefore, novel PFASs identification in cord blood and their relationships with birth outcomes are essential to evaluate prenatal exposure risk of PFASs. Herein, 16 legacy and 12 novel PFASs were identified in 326 cord blood samples collected from pregnant women in Jinan, Shandong, China. The presence of perfluoropolyether carboxylic acids, hydrogen-substituted polyfluoroetherpropane sulfate, and 3:3 chlorinated polyfluoroalkyl ether alcohol in cord blood was reported for the first time. Two extensive OECD (Organization for Economic Co-operation and Development)-defined PFASs named fipronil sulfone and 2-chloro-6-(trifluoromethyl)pyridine-3-ol were also identified. Quantification results showed that the emerging and OECD-defined PFASs separately accounted for 9.4 and 9.7% of the total quantified PFASs, while the legacy PFOA, PFOS, and PFHxS were still the most abundant PFASs with median concentrations of 2.12, 0.58, and 0.37 ng/mL, respectively. Several PFASs (C9-C12 PFCAs, C6-C8 PFSAs, and 6:2 Cl-PFESA) showed significantly higher levels for older maternities than younger ones. PFHxS levels were positively associated with birth weight and ponderal index (p < 0.05). The results provide comprehensive information on the presence and exposure risks of several novel PFASs during the early life stage.