A series of novel protic ionic liquids were immobilized on alanine, a cheap readily available amino acid. These short aliphatic chain ionic liquids have a low cost of preparation, a low toxicity, and need simple synthesis/purification processes. Their catalytic activity was tested for citral–acetone and benzaldehyde–acetone condensations, two reactions with an interest for pharmacological as well as flavor and fragrance industry. Good results were obtained in terms of conversion and selectivity; moreover, the catalysts can be recycled and reused for several consecutive cycles without significant loss of activity.