To assess the impact of conversion of native forests to monocultural larch plantations on soil chemical properties, we compared the total and various fractions of soil phosphorus (P) and acid phosphatase activity (APA) between natural secondary forests (NSF) and Larix olgensis plantations (LOP) on a montane forest site in eastern Liaoning Province, Northeast China. We found that the concentrations of total P (TP), inorganic P, and iron-bound P (Fe-P) were significantly higher, and the concentrations of microbial biomass P (MBP), sodium bicarbonate-extractable organic P (NaHCO3-Po), and APA were significantly lower, in the LOP stands than in the NSF stands; whilst organic P, sodium bicarbonate-extractable inorganic P (NaHCO3-Pi), aluminum-bound P (Al-P) and calcium-bound P (Ca-P) were comparable between the two forest types. Our study also showed that the ratios of MBP/TP, NaHCO3-Pi/TP, NaHCO3-Po/TP, and APA significantly varied with time during the growing season. Moreover, the concentrations of NaHCO3-Pi, NaHCO3-Po, and MBP had significant (P < 0.01) and positive linear relationships with APA. Overall, results from this study suggest that conversion of native forests to larch plantations in the region is more likely to cause compositional change in soil P than to result in reduction in overall P availability.