Dangling bonds (DBs) are common defects in silicon that affect its electronic performance by trapping carriers at the in-gap levels. For probing the electrical properties of individual DBs, a scanning tunneling microscope (STM) is an effective instrument. Here we study transitions between charge states of a single DB on chlorinated and brominated Si(100)-2 × 1 surfaces in an STM. We observed transitions between positively and negatively charged states of the DB, without the participation of the neutral state. We demonstrated that the (+/-) transition occurs when the DB and substrate states are out of equilibrium. This transition is related to the charge neutrality level (CNL), which indicates a change in the DB's character from donor-like to acceptor-like. The STM voltage at which the (+/-) transition took place varied depending to the electrostatic environment of the DB. Our results complement the understanding of the electronic properties of the DBs, and they should be taken into account in applications that use charge manipulation on the DBs.