Bletilla ochracea Schltr. polysaccharides (BOP) have a similar structure to Bletilla striata (Thunb.) Reichb.f. (Orchidaceae) polysaccharides (BSP). Therefore, BOP can be considered as a substitute for BSP in the food, pharmaceuticals and cosmetics fields. To the best of our knowledge, little information is available regarding the optimization of extraction and antioxidant activity of BOP. In this study, response surface methodology (RSM) was firstly used for optimizing the extraction parameters of BOP. The results suggested that the optimal conditions included a temperature of 82 °C, a duration of 85 min and a liquid/material ratio of 30 mL/g. In these conditions, we received 26.45% ± 0.18% as the experimental yield. In addition, BOP exhibited strong concentration-dependent antioxidant abilities in vitro. The half-maximal effective concentration (EC50) values of BOP against 1,1-diphenyl-2-picrylhydrazyl (DPPH·), 2,2′-azino-bis (3-ethylbenzothiazoline-6-sulphonate) (ABTS+·), hydroxyl (·OH) and superoxide anion (·O2−) radicals and ferrous ions (Fe2+) were determined as 692.16, 224.09, 542.22, 600.53 and 515.70 µg/mL, respectively. In conclusion, our results indicate that BOP can be a potential natural antioxidant, deserving further investigation.