Aim at CO exceed the standard of Kailuan mining, collected 22 typical coal samples, study the relationship between H/C, O/C and fa, 2 (R-1) /C.with coal macerals, Relationship between H/C and vitrinite is concave curve, and negatively correlated with vitrinite , a convex curve with minerals; O/C associated with vitrinite positively, negatively correlated with vitrinite and exinite, negatively related, and mineral matter in coal is curve form; fa is a concave curve with vitrinite, was three times curve with vitrinite and with exinite is not obvious, a convex the curve form and coal mineral. Research show: inertinite contribution of coal generation's CO larger, vitrinite adsorbate CO greater , vitrinite content of less than 50%, vitrinite is a greater impact on the coal molecular structure, effect of vitrinite in coal molecular structure of coal molecular structure may occur; the rearrangement, during metamorphism isomerism, with CO seam may at this time.