Noncentrosymmetric (NCS) tetrel pnictides have recently generated interest as nonlinear optical (NLO) materials due to their second harmonic generation (SHG) activity and large laser damage threshold (LDT). Herein nonmetal‐rich silicon phosphides RuSi4P4 and IrSi3P3 are synthesized and characterized. Their crystal structures are reinvestigated using single crystal X‐ray diffraction and 29Si and 31P magic angle spinning NMR. In agreement with previous report RuSi4P4 crystallizes in NCS space group P1, while IrSi3P3 is found to crystallize in NCS space group Cm, in contrast with the previously reported space group C2. A combination of DFT calculations and diffuse reflectance measurements reveals RuSi4P4 and IrSi3P3 to be wide bandgap (Eg) semiconductors, Eg = 1.9 and 1.8 eV, respectively. RuSi4P4 and IrSi3P3 outperform the current state‐of‐the‐art infrared SHG material, AgGaS2, both in SHG activity and laser inducer damage threshold. Due to the combination of high thermal stabilities (up to 1373 K), wide bandgaps (≈2 eV), NCS crystal structures, strong SHG responses, and large LDT values, RuSi4P4 and IrSi3P3 are promising candidates for longer wavelength NLO materials.