Soils on many smallholder farms in Southern Africa are severely depleted in plant nutrients, in particular phosphorus (P), following years of maize monocropping with little or no fertilizer input. Past studies suggest that pigeon pea (Cajanus cajan (L.) Millsp.) may increase plant-available P. Pigeon pea is not a common crop in much of Southern Africa, and the effect of locally grown pigeon pea varieties on plant-available P is unknown. We assessed the changes in plant-available P after growing pigeon pea varieties MPPV-2, MPPV-3, and Babati White in Zambia, viz. Lixisols of Choma and Mkushi, Acrisols of Chipata and Kasama, and Arenosols of Kaoma. The selected soils were not fertilized. Baseline soils (0–20 cm), sampled after long-term maize monocropping and soils from the same fields after growing pigeon pea were collected from field trials in Kaoma, Chipata, Choma, and Mkushi and analyzed for plant-available P. Further, a greenhouse study was conducted with soils from Kasama, Choma, Kaoma, and Chipata, under which soil P was determined before and after growing pigeon pea, soybean (Dina), and maize (SC 419) without fertilizer addition. Pigeon pea under field studies had no significant (p > 0.05) effect on plant-available P in Choma, Kaoma, and Chipata. In Mkushi, pigeon pea cropping resulted in a 47.5% significant decline (p ≤ 0.05) in plant-available P, amounting to a loss of 11.2 kg ha−1. The greenhouse study showed a significant decline (p ≤ 0.001) in plant-available P after seven weeks of maize growth, while there was no significant (p > 0.05) effect on plant-available P after soybean and pigeon pea cropping. The latter was primarily due to the significantly higher P uptake associated with larger biomass production of maize after seven weeks in the greenhouse. During the initial seven weeks, pigeon pea biomass had significantly higher P concentrations than maize. Thus, P deficiency symptoms were exhibited in maize, while pigeon pea appeared healthy. However, mobilized P, calculated as the sum of plant P and soil P after cropping minus soil P before planting, was significantly lower (p ≤ 0.01) in pigeon pea compared to soybean and maize. Synthesizing field and greenhouse experiments suggests that there is a low net decline of plant-available P from soils after pigeon pea cropping. Therefore, rotation with these pigeon pea varieties could be beneficial to resource-poor farmers due to low P removal and its ability to grow in P-deficient soil.