Abstract: The LHCf experiment aims to improve knowledge of forward neutral particle production spectra at the LHC energy which is relevant for the interpretation of air shower development of high energy cosmic rays. Two detectors, each composed of a pair of sampling and imaging calorimeters, have been installed at the forward region of IP1 to measure pi(0) energy spectra above 600 GeV. In this paper, we present a Monte Carlo study of the pi(0) measurements to be performed with one of the LHCf detectors for proton-proton collisions at root s = 14 TeV. In approximately 40 min of operation at luminosity 0.8 x 10(29) cm(-2) s(-1) during the beam commissioning phase of LHC, about 1.5 x 10(4) pi(0) events are expected to be obtained at two transverse positions of the detector. The backgrounds from interactions of secondary particles with beam pipes and interactions of beam particles with residual gas in the beam pipes are expected to be less than 0.1% of the signal from pi(0)s. We also discuss the capability of LHCf measurements to discriminate between the various hadron interaction models that are used for simulation of high energy air showers, such as DPMJET3.03, QGSJETII-03, SIBYLL2.1 and EPOS1.99.