Leon Levavasseur's Antoinette engine used by Santos Dumont in the 14Bis had direct petrol injection.
From CentennialofFlight,gov:
The Antoinette engine was designed and built in France by Léon Levavasseur. Named after the designer's daughter, it was Europe's most widely used engine until 1909-1910. The first Antoinette engine dated from about 1901 and was used in a speedboat. By 1905, Levavasseur had produced a water-cooled engine with eight-cylinders arranged in a 90-degree "V" and with direct fuel injection. It was safe, strong, and fairly powerful, generating 50 horsepower (37 kilowatts) and weighing about 110 pounds (50 kilograms). Its power-to-weight ratio was not surpassed for 25 years.