Abstract We present $∼ {0.^{\prime \prime }3}$ (114 pc) resolution maps of [C i] 3P1–3P0 (hereafter [C i] (1–0)) and 12CO (1–0) obtained toward Arp 220 with the Atacama Large Millimeter/submillimeter Array. The overall distribution of the [C i] (1–0) emission is consistent with the CO (1–0). While the [C i] (1–0) and CO (1–0) luminosities of the system follow the empirical linear relation for the unresolved ULIRG sample, we find a sublinear relation between [C i] (1–0) and CO (1–0) using the spatially-resolved data. We measure the [C i] (1–0)$/$CO (1–0) luminosity ratio per pixel in star-forming environments of Arp 220 and investigate its dependence on the CO (3–2)$/$CO (1–0) ratio (RCO). On average, the [C i] (1–0)$/$CO (1–0) luminosity ratio is almost constant up to RCO ≃ 1 and then increases with RCO. According to the radiative transfer analysis, a high C i$/$CO abundance ratio is required in regions with high [C i] (1–0)$/$CO (1–0) luminosity ratios and RCO > 1, suggesting that the C i$/$CO abundance ratio varies at ∼100 pc scale in Arp 220. The [C i] (1–0)$/$CO (1–0) luminosity ratio depends on multiple factors and may not be straightforward to interpret. We also find the high-velocity components traced by [C i] (1–0) in the western nucleus, likely associated with the molecular outflow. The [C i] (1–0)$/$CO (1–0) luminosity ratio in the putative outflow is 0.87 ± 0.28, which is four times higher than the average ratio of Arp 220. While there is a possibility that the [C i] (1–0) and CO (1–0) emission traces different components, we suggest that the high line ratios are likely to be because of elevated C i$/$CO abundance ratios based on our radiative transfer analysis. A C i-rich and CO-poor gas phase in outflows could be caused by the irradiation of the cosmic rays, the shock heating, and the intense radiation field.