In this paper, a comprehensive study of the effects of Ni-doping on structural, electrical, thermal and magnetic properties of the NbB2 is presented. Low amounts (leq 10 %) of Ni substitution on Nb sites cause structural distortions and induce drastic changes in the physical properties, such as the emergence of a bulk superconducting state with anomalous behaviors in the critical fields (lower and upper) and in the specific heat. Ni-doping at the 9 at.% level, for instance, is able to increase the critical temperature (TC) in stoichiometric NbB2 (< 1.3 K) to approximately 6.0 K. Bulk superconductivity is confirmed by magnetization, electronic transport, and specific heat measurements. Both Hc1 and Hc2 critical fields exhibit a linear dependence with reduced temperature (T/TC), and the specific heat deviates remarkably from the conventional exponential temperature dependence of the single-band BCS theory. These findings suggest multiband superconductivity in the composition range from 0.01 leq x leq 0.10.