Biocatalytic accumulation, followed by chronoamperometric detection, is shown to greatly enhance the sensitivity of mediatorless biosensing of hydrogen peroxide at horseradish peroxidase (HRP)/carbon paste bioelectrodes. The mixed carbon paste, with its close proximity between the biocatalytic and graphite sensing sites, promotes the mediatorless accumulation of the oxidized form of HRP. Hence, a 28-fold enhancement of the response for 10 muM hydrogen peroxide is obtained following 3-minute preconcentration. The relative standard deviation (surface-to-surface) at the 10 muM level is 3.3%. The effect of experimental variables, such as the preconcentration time, measuring potential, or paste composition, are explored. Analogous observations are reported for tissue (horseradish root)-based carbon pastes, for mediated HRP detection, and for monitoring of organic peroxides. Future prospects of the bioamplification approach are discussed.