Fibrotic atrial cardiomyopathy is characterized by a replacement of healthy atrial tissue with diffuse patches exhibiting slow electrical conduction properties and altered myocardial tissue structure, which provides a substrate for the maintenance of reentrant activity during atrial fibrillation (AF). Therefore, an early detection of atrial fibrosis could be a valuable risk marker for new-onset AF episodes to select asymptomatic subjects for screening, allowing for timely intervention and optimizing therapy planning. We examined the potential of estimating the fibrotic tissue volume fraction in the atria based on P waves of the 12-lead ECG recorded in sinus rhythm in a quantitative and non-invasive way. Our dataset comprised 68,282 P waves from healthy subjects and 42,227 P waves from AF patients with low voltage areas in the atria, as well as 642,400 simulated P waves of a virtual cohort derived from statistical shape models with different extents of the left atrial myocardium replaced by fibrosis. The root mean squared error for estimating the left atrial fibrotic volume fraction on a clinical test set with a neural network trained on features extracted from simulated and clinical P waves was 16.57%. Our study shows that the 12-lead ECG contains valuable information on atrial tissue structure. As such it could potentially be employed as an inexpensive and widely available tool to support AF risk stratification in clinical practice.