The high-voltage spinel ${\mathrm{LiNi}}_{0.5}{\mathrm{Mn}}_{1.5}{\mathrm{O}}_4$ (LNMO) is a promising cobalt-free cathode material for lithium-ion batteries, yet its integration as a binder-free thin film on metallic current collectors via simple solution routes remains underexplored. Here, LNMO films were synthesized on 304 stainless steel (SS304) by metal–organic decomposition (MOD) from metal–acetate precursors in ethanol, followed by spin-coating and annealing at 500, 600, and 700 °C under flowing ${\mathrm{O}}_2$. The films were characterized by XRD, FESEM–FIB cross-sectioning, EDS, and XPS, and tested as binder-free cathodes by cyclic voltammetry and galvanostatic charge/discharge. All samples are dense, approximately 1.9 μm thick, and crystallize in the disordered spinel phase. The LNMO crystallite size increases from 21.9 to 43.8 nm between 500 and 700 °C, while the grain size also shows a temperature dependence, increasing the average size from 25 up to 56 nm in diameter. XPS confirms ${\mathrm{Mn}}^{4+}$ as the dominant manganese surface species (45–49%) across all samples. The films deliver reversible discharge capacities of 92, 92, and 70 mAh ${\mathrm{g}}^{-1}$ at 0.1 C for LNMO500, LNMO600, and LNMO700, respectively, with well-defined ${\mathrm{Ni}}^{2+}{\mathrm{/Ni}}^{3+}$ and ${\mathrm{Ni}}^{3+}{\mathrm{/Ni}}^{4+}$ redox peaks at 4.7 and 4.8 V. DFT calculations independently predict a voltage plateau at ∼4.7 V for $0.2\le x\le 1$, in agreement with the experimental profiles. These findings establish MOD as a viable, vacuum-free route to the synthesis of nanostructured LNMO cathodes.