La3+-doped BaSnO3 microtubes (La3+–BaSnO3) have been synthesized by electrospinning method, and the influence of La3+ content on the sensing properties of BaSnO3 for detection of formaldehyde vapor has been investigated. The as-prepared materials have been characterized using XRD, SEM, DSC, XPS, and UV-Vis. The La3+–BaSnO3 sample doped with 4 wt% La exhibited a response as high as 220 to formaldehyde vapor (1000 ppm concentration) along with a very low detection limit of 0.1 ppm at 270 °C, whereas at 140 °C, it exhibited a response of 80 and detection limit of 1 ppm. In addition, the sensor showed excellent selectivity of 57 to formaldehyde at 140 °C when compared with other vapors. Further, the sensor also showed good repeatability and stability over a long period of time suggesting its strong potential as a commercial formaldehyde sensor.