The diffusion and activation of implanted boron in silicon during rapid thermal annealing (RTA) has been studied using the analytical techniques of SIMS, TEM, and sheet resistance measurements. Both crystalline and pre-amorphised silicon substrates were investigated. Data analysis in conjunction with a range of numerical models indicates some novel features of boron RTA, as well as accounting for previously observed features. In particular, a large transient diffusion enhancement coupled with an increase of electrical activity, are seen at short anneal times, in the case of crystalline silicon substrates. A non-equilibrium diffusion enhancement of a different type is also seen at much longer times, in both crystalline and pre-amorphised samples implanted to high doses. This second enhancement persists after all the precipitated boron formed on implantation has become substitutional. TEM studies show that the transient enhancement may be associated with the evolution of extended defect structures during the early stages of annealing. Both types of enhancement can be well represented by multiplying the ‘normal’ concentration-dependent diffusivity (with β=0.5) by a factor f>1.