Deep defects in the long-wave infrared (LWIR) HgCdTe heterostructure photodiode were measured via deep-level transient spectroscopy (DLTS) and photoluminescence (PL). The n+-P+-π-N+ photodiode structure was grown by following the metal-organic chemical vapor deposition (MOCVD) technique on a GaAs substrate. DLTS has revealed two defects: one electron trap with an activation energy value of 252 meV below the conduction band edge, located in the low n-type-doped transient layer at the π-N+ interface, and a second hole trap with an activation energy value of 89 meV above the valence band edge, located in the π absorber. The latter was interpreted as an isolated point defect, most probably associated with mercury vacancies (VHg). Numerical calculations applied to the experimental data showed that this VHg hole trap is the main cause of increased dark currents in the LWIR photodiode. The determined specific parameters of this trap were the capture cross-section for the holes of σp = 10-16-4 × 10-15 cm2 and the trap concentration of NT = 3-4 × 1014 cm-3. PL measurements confirmed that the trap lies approximately 83-89 meV above the valence band edge and its location.