The effects of Al microparticles on plasma chemistry and structural dynamics of laser-ablated pure and aluminized 5-methyl-1H-tetrazole (C₂H₄N₄) are investigated with nanosecond laser induced breakdown spectroscopy (LIBS). Time-resolved and time-integrated emission spectra of the CN violet system (B²Σ⁺ − X²Σ⁺, Δν = 0 sequence) and C₂ swan system (d³Π_g − a³Π_u, Δν = 0 sequence) are obtained and analyzed. The intensities of the CN and C₂ emissions are increased by the Al microparticles, and their lifetimes in the laser-induced plasma are also altered. Furthermore, spatially and temporally resolved imaging measurements of the CN and C₂ emissions are also conducted. The addition of Al microparticles leads to facilitated expansion and splitting of the laser-induced plasma.