Isothermal devitrification of Pd85Si15 amorphous alloys has been analyzed using differential scanning calorimetry (DSC) and x-ray diffractometry. Both as-quenched and aged amorphous ribbons were investigated. Crystallization of aged samples starts from the surface and proceeds several micrometers into the bulk. The product of this process is a layer of strongly textured palladium (111) followed by a mixture of Pd2Si, Masumoto MSI phase, and untextured palladium. Next, the crystallization occurs via a different (bulk) mechanism, resulting in a mixture of Masumoto MSII phase and untextured palladium. The bulk mechanism is the only one observed in as-quenched samples. The surface and bulk crystallization mechanisms are spatially decoupled and, therefore, the corresponding DSC data can be analyzed separately. This has been done according to the Kolmogorov–Johnson–Mehl–Avrami model and also using the recently developed concept of local value of Avrami exponent n. For both the surface and bulk crystallization the phase transition process cannot be characterized by a single value of n. Observed variation of n with the crystallized fraction x is explained by a considerable variation of the nucleation rate that takes place during devitrification.