We present the results of simultaneous radio and X-ray observations of PSR J1819-1458. Our 94-ks XMM-Newton observation of the high magnetic field 5*10^13 G pulsar reveals a blackbody spectrum (kT~130 eV) with a broad absorption feature, possibly composed of two lines at ~1.0 and ~1.3 keV. We performed a correlation analysis of the X-ray photons with radio pulses detected in 16.2 hours of simultaneous observations at 1-2 GHz with the Green Bank, Effelsberg, and Parkes telescopes, respectively. Both the detected X-ray photons and radio pulses appear to be randomly distributed in time. We find tentative evidence for a correlation between the detected radio pulses and X-ray photons on timescales of less than 10 pulsar spin periods, with the probability of this occurring by chance being 0.46%. This suggests that the physical process producing the radio pulses may also heat the polar-cap. ; Comment: 12 pages, 5 figures, Accepted to ApJ