The purpose of this study was to investigate the effects of microwave power and additives on the microwave-assisted pyrolysis of cotton stalk. Pyrolysis temperature profiles, product yields, and bio-oil components were analyzed. The results indicated that as the microwave power increased, so did the final temperature and heating rate. When microwave power increased from 800 to 1200 W, the yield of the solid residue decreased and gas yield increased, but the maximum bio-oil yield of 26.7% was achieved under a microwave power of 1000 W. All three of the additives (NaOH, Na2CO3, and H3PO4) increased the yields of solid residue and gas, while the yield of the bio-oil decreased. Gas chromatography-mass spectrometry (GC-MS) analysis indicated that the main components of bio-oil from microwave-assisted pyrolysis of pure sample were acetol, furfural, 2-methoxy-phenol, and 4-methyl-2-methoxy-phenol. Sodium hydroxide and sodium carbonate (NaOH and Na2CO3) greatly favor the formation of acetol. Phosphoric acid (H3PO4) remarkably promoted the formation of furfural and 4-methyl-2-methoxy-phenol, while H3PO4 inhibited the formation of acetol.