We report on the experimental implementation of a polarimeter based on a scheme known to be optimal for obtaining the polarization vector of ensembles of spin-1/2 quantum systems, and the alignment procedure for this polarimeter is discussed. We also show how to use this polarimeter to estimate the polarization state for identically prepared ensembles of single photons and photon pairs and extend the method to obtain the density matrix for generic multi-photon states. State reconstruction and performance of the polarimeter is illustrated by actual measurements on identically prepared ensembles of single photons and polarization entangled photon pairs.