This paper aimed to explore the effect of micro-alloyed Nb on the tribology performance of hypoeutectic gray cast iron. Four disc samples containing different contents of Nb (0, 0.12wt.%, 0.21wt.%, and 0.33wt.%) were fabricated. Non-asbestos resin-based friction materials were selected as counterface. The friction test was performed on a constant speed friction machine under different temperature conditions. Prior to test, the microstructure of discs was observed by SEM and metalloscope. After test, the worn surfaces of friction couples were characterized through SEM. Results showed that the friction coefficient increases firstly and then decreases with the increasing Nb addition. This was determined by the refining effect of Nb on the pearlite matrix. The friction efficiency was adversely influenced by the Nb addition. This was because the as-refined graphite by Nb weakened the heat dissipation capacity. Additionally, the wear resistance of disc increased with the increase of Nb concentration in the range of 0~0.21wt.%, but an obvious decrease at 0.33wt.%. This was closely related to the transformation of wear mechanisms.