The effect of gross fiber characteristics on enzyme accessibility and hydrolysis of Douglas fir kraft pulp substrates was investigated. The average fiber size and coarseness of the substrate had a significant effect on the enzyme adsorption capacity. This was primarily due to the increased specific surface area of small fibers and fines. The observed adsorption capacities were in agreement with the hydrolysis rates and yields because the substrates with the lower average fiber size were hydrolyzed both at a faster rate and more completely. The observed changes in fiber-length distribution and fiber coarseness suggested that the effect of fiber size was most influential during the initial stages of hydrolysis. The small fibers and fines present in heterogeneous, lignocellulosic substrates were hydrolyzed rapidly, yielding a high initial rate of hydrolysis.