We report the magneto-transport properties of an individual single crystalline Bi nanowire grown by a spontaneous growth method. We have successfully fabricated a four-terminal device based on an individual 400-nm-diameter nanowire using plasma etching technique to remove an oxide layer forming on the outer surface of the nanowire. The transverse MR (2496% at 110 K) and longitudinal MR ratios (38% at 2 K) for the Bi nanowire were found to be the largest known values in Bi nanowires. This result demonstrates that the Bi nanowires grown by the spontaneous growth method are the highest-quality single crystalline in the literatures ever reported. We find that temperature dependence of Fermi energy ($E_F$) and band overlap (${ riangle}_0$) leads to the imbalance between electron concentration ($n_e$) and hole concentration ($n_h$) in the Bi nanowire, which is good agreement with the calculated $n_e;and;n_h$ from the respective density of states, N(E), for electrons and holes. We also find that the imbalance of $n_e;and;n_h$ plays a crucial role in determining magnetoresistance (MR) at T<75 K for $R_T$ and at T<205 K for $R_L$, while mean-free path is responsible for MR at T>75 K for $R_T$ and T>205 K for $R_L$.