Monte Carlo simulations were used to investigate the solvation of naphthalene in supercritical carbon dioxide at a temperature of 308.38 K just above the solvent's critical temperature and at pressures of 74.6, 79.7, 87.8, and 310.2 bar covering a range from just below to far above the solvent's critical pressure and at a slightly elevated temperature of 318.15 K and a pressure of 93.0 bar. The Monte Carlo simulations were carried out in the isobaric−isothermal ensemble and employed the transferable potentials for phase equilibria (TraPPE) force field. Systems containing 2000 carbon dioxide molecules and from 0 to 4 solute molecules were used for all five state points, and additional simulations with 16 000 solvent molecules were carried out at the lower temperature and p = 79.7 bar. In agreement with experiment, the simulations yield large, negative partial molar volumes of naphthalene near the critical pressure at 79.7 bar, with values of −4340 ± 750 and −3400 ± 620 cm3 mol-1 for the 2000 and 16 000 molecule systems, respectively. Structural analysis through radial distribution functions and the corresponding number integrals yields good agreement with neutron diffraction data and shows evidence for a long-range density enhancement around solutes but lacking any specific solute−solvent clustering. Solvatochromic shifts estimated from the local solvent structure correlate well with the experimental data over the entire pressure range.