Laser-assisted doping of intrinsic silicon carbide (SiC) films deposited on Si (100) substrates by pulsed laser deposition (PLD) method and its influence on simultaneous annealing of the thin film is studied. PLD grown intrinsic SiC films are transformed to p-type SiC and n-type SiC, using laser-assisted doping in aqueous aluminum chloride and phosphoric solutions, respectively. Simultaneous doping and annealing of the SiC film are observed during laser-assisted doping. By precisely positioning the selectively doped region, lateral p–n diodes are formed on the SiC films without using any mask. Electric characteristics confirmed the formation of a lateral p–n diode structure. Numerical analysis of temperature distribution along the depth of the SiC films explains the mechanism of simultaneous doping and annealing during the laser treatment.