Complex fabrication methods for carbon nanotubes limit their potential for scale-up and use in practical applications. This study developed a simple method to deposit multiwall carbon nanotube (MWCNT) forest-like films from polyacrylonitrile and MWCNT solutions by coaxial electrospray. A MWCNT solution was used as the shell flow to generate vertically aligned tree-like structures at mesoscopic scale (∼10−5 m) on aluminum, silicon, and fiber membrane substrates. These forest-like structures assembled from highly conductive core-shell polymer/MWCNT particles with diameter of about 1 μm. The fabricated MWCNT films show good potential for applications in flexible electronics and as conductive filters.