By means of the first-principles method, the bias effect on the magnetism of polyacene (n-acene) connected to gold electrodes is investigated. A magnetic to nonmagnetic transition for the polyacene (n > 6) is observed when the bias exceeds a critical value. The mechanism is explored as the bias-induced variation of electronic localization, which leads to the exchange of dominant mechanism for molecular magnetism from Columbic interaction between electrons to electron hopping rate. A significant enhancement of the differential conductance and suppression of current spin polarization for the molecular device are also obtained accompanied by the transition of molecular magnetism. This work proposes a feasible way to manipulate the magnetism of polyacene via electric method and reveals the relation between molecular magnetism and its conductance.