Twilio empowers developers to add communication technology to their applications by providing APIs and SDKs for sending SMS and MMS, WhatsApp messages, emails, phone calls, and video calls. To send an SMS from a VB.NET console application, one needs to create a new project, store sensitive secrets such as Account SID and Auth Token using the .NET Secret Manager, load these secrets into the .NET application, and then use Twilio's helper library for .NET to make sending SMS more convenient. The process involves importing necessary namespaces, initializing user secrets, retrieving the two secrets from configuration, printing them to the console, and finally creating a message resource to send an SMS to a personal phone number with a specified body.