A facile route for controlled alignment of electrospun multiwalled carbon nanotube (MWCNT)-reinforced Polyvinyl Alcohol (PVA) nanofibers using slotted collector geometries has been realized. The process is based on analytical predictions using electrostatic field analysis for envisaging the extent of alignment of the electrospun fibers on varied collector geometries. Both the experimental and theoretical studies clearly indicate that the introduction of an insulating region into a conductive collector significantly influences the electrostatic forces acting on a charged fiber. Among various collector geometries, rectangular slotted collectors with circular ends showed good fiber alignment over a large collecting area. The electrospun fibers produced by this process were characterized by Atomic Force Microscopy (AFM), High Resolution Transmission Electron Microscopy (HRTEM), Scanning Electron Microscopy (SEM) and Optical Microscopy. Effects of electrospinning time and slot widths on the fiber alignment have been analyzed. PVA-MWCNT nanofibers were found to be conducting in nature owing to the presence of reinforced MWCNTs in PVA matrix. The method can enable the direct integration of aligned nanofibers with controllable configurations, and significantly simplify the production of nanofibersbased devices.