Annual bluegrass is a problematic weed of Kentucky bluegrass turf that can be selectively controlled with POST applications of primisulfuron-methyl. The objective of this research was to evaluate physiological behavior of primisulfuron-methyl attributed to selectivity in these species. In application placement experiments, annual bluegrass shoot weight reductions from the nontreated from high to low were treatments including: foliar + soil ≥ soil only ≥ foliar. Annual bluegrass averaged 33 and 52% shoot weight reductions from the nontreated after 4 wk from primisulfuron-methyl at 40 and 80 g ha−1, respectively. Kentucky bluegrass shoot weight was not reduced from the nontreated, and application placements were similar. From five harvests ranging 1 to 168 h after treatment (HAT), annual and Kentucky bluegrass absorbed up to 25 and 32% of foliar applied 14C-primisulfuron-methyl, respectively. Both grasses distributed 15% of foliar absorbed 14C to nontreated shoots with minimal translocation (≤ 2%) to roots after 168 h. Annual bluegrass translocated 2 times more root-absorbed 14C to shoots than Kentucky bluegrass at 24, 72, and 168 HAT. From foliar uptake, the time required for annual and Kentucky bluegrass to degrade 50% of the absorbed herbicide to the major metabolite detected (Rf 0.1) measured > 168 and 93 h, respectively. In root metabolism experiments, annual bluegrass had ≈ 3 times and 2 times more primisulfuron acid in roots and shoots, respectively, than Kentucky bluegrass at 24, 72, and 168 HAT. The isolated acetolactate synthase (ALS) enzymes from the two grasses were equally susceptible to inhibition by primisulfuron-methyl. Overall, selectivity of primisulfuron-methyl for annual bluegrass control in Kentucky bluegrass is attributed to differential translocation and metabolism between species.