Studies of the growth of large-area free-standing single-crystalline films of p-quinquephenyl are presented. High-quality crystals were grown by slow cooling of a hot chlorobenzene solution. Worse quality large-area free-standing single crystals of p-quinquephenyl were also grown by using physical vapor transport and used for comparison. The crystal structure of p-quinquephenyl at 293 K and 85 K was refined by single-crystal X-ray diffraction. The optical absorption and photoluminescence spectra of solutions and crystalline films were obtained and analyzed; a positive solvatochromic effect was detected.