The well-known red emitting complex Ir(btp)(2)(acac) (bis(2-(2'-benzothienyl)-pyridinato-N,C-3')iridium(acetylacetonate)), frequently used as emitter material in OLEDs, has been investigated in a polycrystalline CH2Cl2 matrix. The studies were carried out under variation of temperature down to 1.2 K and at magnetic fields up to B = 10 T. Highly resolved emission and excitation spectra of several specific sites are obtained by site-selective spectroscopy. For the preferentially investigated site (I -> 0 at 16268 cm(-1)), the three substates I, II, and III of the T-1 triplet state are separated by Delta EII-I = 2.9 cm(-1) and Delta EIII-I = 25.0 cm(-1), respectively. Delta EIII-I represents the total zero-field splitting (ZFS). The individual decay times of these substates are tau(I) = 150 mu s, tau(II) = 58 mu s, and tau(III) = 2 mu s, respectively. The long decay time of the lowest substate I indicates its almost pure triplet character. The time for relaxation from state II to state I (spin-lattice relaxation, SLR) is as long as 22 mu s at T = 1.5 K, while the thermalization between the two lower lying substates and substate III is fast. Application of a magnetic field induces Zeeman mixing of the substates of T-1, resulting in an increased splitting between the two lower lying substates from 2.9 cm(-1) at zero field to, for example, 6.8 cm(-1) at B = 10 T. Further, the decay time of the B-field perturbed lowest substate I-B decreases by a factor of about 7 up to 10 T. The magnetic field properties clearly show that the three investigated states belong to the same triplet parent term of one single site. Other sites show a similar behavior, though the values of ZFS vary between 15 and 27 cm(-1). Since the amount of ZFS reflects the extent of MLCT (metal-to-ligand charge transfer) parentage, it can be concluded that the emitting state T-1 is a (LC)-L-3 (ligand centered) state with significant admixtures of (MLCT)-M-1,3 (metal-to-ligand charge transfer) character. Interestingly, the results show that the MLCT perturbation is different for the various sites. An empirical correlation between the amount of ZFS and the compound's potential for its use as emitter material in an OLED is presented. As a rule of thumb, a triplet emitter is considered promising for application in OLEDs, if it has a ZFS larger than about 10 cm(-1).