In this work, novel synthesis of palladium altered MnO2 thin films on CNT/Ta sensor electrode by spray pyrolysis technique was demonstrated. The existence of carbon (002) plane and preferential α-MnO2 (110) plane was confirmed from the XRD patterns. SEM micrographs revealed the formation of dense and uniform Pd nanodentrites which were tightly bonded onto the MnO2-nanotube matrix, favourable for H2O2 detection. The Pd modified MnO2 fabricated on the entangled carbon nanotube network displayed a high electrocatalytic activity with an enhanced sensitivity of 116.1 μA mM−1 Cm−2. Also, the hybrid sensor revealed excellent recovery in the range of 99.5–102% when tested in milk samples. Due to the constructive three-dimensional network, the Pd altered MnO2/CNTs/Ta hybrid could provide an ideal platform for H2O2 biosensing in real samples like fruit juices, packaged food, etc.