We provide a new constraint on the small-scale density fluctuations, evaluating the diffuse background free-free emission from dark matter halos in the dark ages. If there exists a large amplitude of the matter density fluctuations on small scales, the excess enhances the early formation of dark matter halos. When the virial temperature is sufficiently high, the gas in a halo is heated up and ionized by thermal collision. The heated ionized gas emits photons by the free-free process. We would observe the sum of these photons as the diffuse background free-free emission. Assuming the analytical dark matter halo model including the gas density and temperature profile, we calculate the intensity of the diffuse background free-free emission from early-formed dark matter halos in the microwave frequency range. Comparing with the recent foreground analysis on cosmic microwave background, we obtain the constraint on the excess of the density fluctuations on small scales. Our constraint corresponds to $P_zeta lesssim 10^{-8}$ for $k simeq 1-100~mathrm{Mpc}^{-1}$ in terms of the curvature perturbation. Therefore, our constraint is the most stringent constraint on the perturbations below $1~rm Mpc$ scales.