We present 10 main-sequence ALPINE galaxies (log (M/M⊙) = 9.2 − 11.1 and SFR = 23 − 190 M⊙ yr−1) at z ∼ 4.5 with optical [O ii] measurements from Keck/MOSFIRE spectroscopy and Subaru/MOIRCS narrow-band imaging. This is the largest such multi-wavelength sample at these redshifts, combining various measurements in the ultra-violet, optical, and far-infrared including [C ii]158μm line emission and dust continuum from ALMA and Hα emission from Spitzer photometry. For the first time, this unique sample allows us to analyse the relation between [O ii] and total star-formation rate (SFR) and the interstellar medium (ISM) properties via [O ii]/[C ii] and [O ii]/Hα luminosity ratios at z ∼ 4.5. The [O ii]−SFR relation at z ∼ 4.5 cannot be described using standard local descriptions, but is consistent with a metal-dependent relation assuming metallicities around $50{{\ \rm per\ cent}}$ solar. To explain the measured dust-corrected luminosity ratios of $\log (L_{\rm [OII]}/L_{\rm [CII]}) \sim 0.98^{+0.21}_{-0.22}$ and $\log (L_{\rm [OII]}/L_{\rm H\alpha }) \sim -0.22^{+0.13}_{-0.15}$ for our sample, ionisation parameters log (U) < −2 and electron densities $\log (\rm n_e / {\rm [cm^{-3}]}) \sim 2.5-3$ are required. The former is consistent with galaxies at z ∼ 2 − 3, however lower than at z > 6. The latter may be slightly higher than expected given the galaxies’ specific SFR. The analysis of this pilot sample suggests that typical log (M/M⊙) > 9 galaxies at z ∼ 4.5 to have broadly similar ISM properties as their descendants at z ∼ 2 and suggest a strong evolution of ISM properties since the Epoch of Reionisation at z > 6.