The rate at which phosphocreatine (PCr) is resynthesized after exercise is related to muscle oxidative capacity (Vmax). With the use of a one-dimensional image-guided, localized nuclear magnetic resonance spectroscopy technique, PCr kinetics were monitored in the medial gastrocnemius of eight healthy subjects after voluntary, short duration, maximal rate exercise. Localized spectra were obtained every 6 s with <5% contamination from nonselected regions. Maximal rate exercise elicited near-maximal to maximal muscle activation, as indicated by the high-PCr hydrolysis rate (2.26 +/- 0.07 mM/s) and extensive PCr depletion. At the end of 9 s of maximal rate exercise, PCr was depleted by 61.4 +/- 2.4% and intracellular pH was 7.04 +/- 0.03. After 9 s of maximal rate exercise, PCr recovered with a rate constant (kPCr) of 1.87 +/- 0.15 min(-1) and a Vmax of 67.2 +/- 6.0 mM/min. Independent of prior activity, aerobic ATP synthesis rates reached 48.6 +/- 4.9 mM/min within 9 s. Extending maximal rate exercise to 30 s resulted in 92.0 +/- 1.2% PCr depletion and an intracellular pH of 6.45 +/- 0.07. The intracellular acidosis separated the direct relationship between kPCr and muscle Vmax but did not affect the initial PCr resynthesis rate.