This study compared oxidative delignification of birch kraft pulp fibers to pulp fibers from acid hydrotropic fractionation (AHF) using p-toluenesulfonic acid (p-TsOH). Under oxygen delignification at 20% consistency, AHF pulps with lower hemicellulose content showed higher delignification than kraft pulps with similar lignin content despite its residual lignin (cellulosic enzymatic lignin, CEL) being less reactive with fewer β-O-4 ether aryl linkages based on 2D13C-1 H nuclear magnetic resonance (NMR) spectroscopy. The water retention value (WRV) of AHF pulp fibers, a measure of fiber accessibility to water or oxidative chemicals, was substantially greater than that of kraft pulp fibers. Similar comparison of various AHF pulps further suggested that fibers with lower hemicellulose content were easier to delignify (bleach) despite having more lignin with lower reactivity (fewer β-O-4 linkages). Additionally, the present study also indicated that oxygen delignification was more effective at high fiber consistency, which can be attributed to thinner water films on the fiber surfaces at higher fiber loadings. These results indicated that mass transfer was the rate controlling process in oxidative delignification of wood fibers.